Polycarbonate diol and producing method thereof, and polyurethane and active energy ray-curable polymer composition both formed using same

ABSTRACT

The present invention provides a novel polycarbonate diol and a polyurethane using the polycarbonate diol as raw materials. The novel polycarbonate diol produces polycarbonate diol-based polyurethane which has a high degree of hardness, superior abrasion resistance, and superior hydrophilicity, and is usable for an application such as a paint, a coating agent, a synthetic leather, an artificial leather, and a highly-functional elastomers, or the like. The present invention also provides an active-energy radiation curable polymer composition giving a cured film having a superior contamination resistance and high degree of hardness. The present invention is obtained, for example, by reacting specific two types of diols with diester carbonate in the presence of a transesterification catalyst being a compound using a metal of Group 1 or 2 on the periodic table. The present invention provides a polycarbonate diol wherein the metal content of the transesterification catalyst is 100 weight ppm or less, a polyurethane obtainable by using this polycarbonate diol and an active-energy radiation curable polymer composition containing the urethane(meth)acrylate oligomer which is obtained from the polycarbonate diol.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a Continuation of U.S. Ser. No. 13/652,070,filed Oct. 15, 2012, now allowed, which is a Continuation ofInternational application PC/JP2011/059206, filed Apr. 13, 2011. Thepresent application further claims priority to Japanese applicationJP2010-093155, filed Apr. 14, 2010, and to Japanese applicationJP2010-191858, filed Aug. 30, 2010.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a novel polycarbonate diol. Thisinvention further relates to a polycarbonate-type polyurethane, which ismade of this polycarbonate diol and which is useful for variousapplications such as paints, coating agents, synthetic/artificialleathers, and highly-functional elastomer, etc. with excellent balanceof physical properties.

This invention further relates to an active-energy radiation curablepolymer composition containing an urethane(meth)acrylate oligomer, acured film obtained by irradiating the active energy ray to thecomposition, and a laminated product using the same.

Description of the Related Art

Conventional raw materials of a soft segment part of an industrialscale-produced polyurethane resin are mainly classified into an ethertype typified by polytetramethyleneglycol, an ester type typified byadipate-based ester, polylactone type typified by polycaprolactone andpolycarbonate type typified by polycarbonate diol (Katsuji Matsunaga(editor) “POLYURETIHANE NO KISO TO OUYOU” CMC Publishing CO., LTD.,November 2006, pp. 96-106.).

Among them, the ether type is excellent in hydrolysis resistance,flexibility and stretching properties, while is said to be inferior inheat resistance and light resistance. On the other hand, the ester typehas better heat resistance and weather resistance, while its ester partis inferior in hydrolysis resistance and can not be used in someapplications. On the other hand, the polylactone type is regarded as amore excellent grade in hydrolysis resistance when relative to the estertype, while it also contains an ester group therefore the completecontrol of hydrolysis suppression is impossible. An application ofcombining the ester type, the ether type and the polylactone type isproposed, however any conventional method cannot fully complement thoseweakness.

On the other hand, the polycarbonate-type polyurethane using apolycarbonate diol is recognized as the best quality durable grade interms of heat resistance and hydrolysis resistance, which is widely usedas a durable film, an artificial leather for cars and furnitures, acoating material (especially an water-based coating material), a coatingagent, and an adhesive agent.

However, a polycarbonate diol being commercially and broadly availableis mainly a polycarbonate diol that be synthesized from a1,6-hexanediol, and the polyurethane produced with said polycarbonatediol has a defect in which it is flexible because of a chained softsegment part and its surface is easily bruised physically. Therefore,when the obtained polyurethane is used as a painting material or acoating agent, it may be easily bruised due to physical factors andresult in an inferior appearance.

In order to solve these problems, as a polycarbonate diol which canprovide a polyurethane with higher rigidity, a polycarbonate diolobtained from 1,4-cyclohexanedimethanol (Japanese laid open Sho-55-56124A) as well as a polycarbonate diol obtained from1,4-cyclohexanedimethanol and a 1,6-hexanediol (Japanese laid open2002-69166 A) are proposed.

However, the 1,4-cyclohexanedimethanol is a mixture of a cis-isomer anda trans-isomer due to its producing limitation, and when its mixtureratio is changed, physical properties of the polycarbonate diol itselfbeing synthesized and the polyurethane to be induced will change,therefore its quality control becomes difficult. In addition, apolycarbonate diol, that is obtained by combining the 1,4-cyclohexanedimethanol and the 1,6-hexanediol, exhibits higher hydrophobic propertydue to its structure, so when water-based polyurethane, which has beenknown these days in terms of reduction in environmental burden, isproduced, the hydrophilic structure must be introduced in producing apolyurethane in order to render the polyurethane water-soluble. As aresult, this has been a constraint on polyurethane designing.

The 1,4-cyclohexane dimethanol also has a cyclohexane ring in a moleculeas a ring structure, while the cyclohexane dimethanol is a flexible ringstructure and its hydroxyl is bound to the cyclohexane dimethanol via amethylene group, so its molecular structure is not very rigid and it wasnot enough in terms of the polyurethane hardness to be obtained.Furthermore, the 1,4-cyclohexane dimethanol is derived from a fossilsource, and burning a polymer substance made of this may cause a problemwhich could promote global warming.

Consequently, the development of a polycarbonate diol, which can beeasily produced without those limitations, of which environmental burdenis small, and which exhibits rigid and scratch resistant characteristicwhen a polyurethane is made thereof, has been expected.

On the other hand, isosorbide is a plant-derived diol which is obtainedby cyclodehydrating a sorbitol which is a natural sugar, and is still acompound with small environmental burden even after it is burnt.Therefore, its application has been greatly considered these days as amonomer source for obtaining a polycarbonate with smaller effect onglobal warming (WO 08/029746, for example). According to this WO08/029746, a copolymerized polycarbonate can be produced from a diolmixture containing the isosorbide, which could produce a polycarbonatehaving both handling property and rigid physical property together.

However as a matter of course, a large number of known documents relatedto producing a polycarbonate from the isosorbide all aim to obtain ahigh-molecular weight polycarbonate. Further these documents do notdescribe any isolation approach with high purity of polycarbonate havingsmaller molecular weight and a hydroxyl structure at both ends thereof,and do not describe using isosorbide as a polyol material for producinga polyurethane, either.

On the other hand, coating by paint is a common practice with an aim forprotecting the surface of base material and for maintaining itsappearance. For these paints, a paint material cured by an energy rayirradiation is developed and has been in practical use in terms ofhigher productivity and better working environments, etc.

As a paint material like this, known is an energy ray curable polymercomposition containing an urethane acrylate which is obtained byreaction of an organic polyisocyanate, a polycarbonate polyol having analicyclic structure, a (meth)acrylate having one or more hydroxyl(s) ina molecule, for example. A paint material like this is required variouskinds of characteristics according to applications.

SUMMARY OF THE INVENTION

The first problem of the present invention is to develop a polyurethanewhich is rigid, is not physically easily bruised, and has no designinglimitation for introducing a hydrosoluble structure in producing apolyurethane, and is consequently to design and produce a polycarbonatediol raw material which can exhibit those characteristics for thispurpose. In particular, the second problem is to design and produce apolycarbonate diol raw material to obtain a homogeneous polyurethane. Inaddition, the third problem is to design and produce a polycarbonatediol raw material to obtain a polyurethane having the characteristicsbeing designed.

The forth problem of the present invention is to establish a method forproducing the polycarbonate diol and polyurethane on an industrialscale.

Furthermore, the fifth problem of the present invention is to provide anactive-energy radiation curable polymer composition giving a cured filmhaving an excellent contamination resistance and high degree ofhardness. In particular, the sixth problem is to provide anactive-energy radiation curable polymer composition excellent in coatingproperties.

The inventors of the present invention devoted themselves to researchesto solve the above first, second and forth problems, found that theabove first, second and forth problems can be solved by a polycarbonatediol which is obtained by reacting a specific compound under thepresence of a catalyst, and which has a certain amount of theaforementioned catalyst, and a polyurethane which is produced by usingthis polycarbonate diol, and reached the present invention. Theinventors of the present invention devoted themselves to researches tosolve the above first, third and forth problems, found that the abovefirst, third and forth problems can be solved by a polycarbonate diol,which has a specific repeating unit in a molecular chain and which hasthe specific ratio of the aforementioned specific repeating unit ratioto the molecular chain terminals, and a polyurethane which is producedby using this polycarbonate diol, and reached the present invention.

The inventors of the present invention devoted themselves toconsideration to solve the aforementioned 5 and 6 problems, found thatan active-energy radiation curable polymer composition containing anurethane(meth)acrylate oligomer which is obtained from a raw materialcontaining a polycarbonate diol, in which the average number of hydroxylgroups of the aforementioned polycarbonate diol per one molecule isspecified to a predetermined amount, could result in better coatingproperties. Further the inventors of the present invention found thatwhen a cured film is obtained by curing this, its contaminationresistance and degree of hardness are more particularly excellent than aconventional one, and reached the present invention.

Therefore, the first aspect of the present invention consists in thefollowing [1] to [33].

[1] A polycarbonate diol being obtained by reacting (i) at least one ofdiols selected from isosorbide, isomannide and isoidide, (ii) a diolhaving 1 to 15 carbons which may contain hetero atom, and (iii) adiester carbonate, by use of a transesterification catalyst,

in which the transesterification catalyst is either a compound using ametal of Group 1 or a compound using a metal of Group 2 on the periodictable and,

the amount of the transesterification catalyst contained in thepolycarbonate diol is 100 ppm or less as the weight ratio of the metal.

[2] The polycarbonate diol according to [1], the amount of thetransesterification catalyst contained in the polycarbonate diol is 0.1ppm or more as the weight ratio of the metal.[3] The polycarbonate diol according to [1] or [2], thetransesterification catalyst is a compound using a metal of Group 2 onthe periodic table.[4] The polycarbonate diol according to any one of [1] to [3], in whichat least part of a molecular chain includes a repeating unit representedby the following formula (A) and a repeating unit represented by thefollowing formula (B) and,

the number average molecular weight is 250 or more and 5,000 or less,and

the terminal (A) ratio represented by the following formula (I) is 1.2or more and 1.9 or less.

Terminal (A) ratio (I)−{(The number of structure (A) in molecular chainterminal)/(The total number of structures (A) and (B) in molecular chainterminal)}/{(The number of structure (A) in molecular chain)/(The totalnumber of structures (A) and (B) in molecular chain)}  [Mathematicalformula 1]

In formula (B), X represents a divalent group having 1 to 15 carbonswhich may contain hetero atom.[5] The polycarbonate diol according to any one of [1] to [4], in whichthe highest temperature of the reaction is lower than 180° C.[6] A polycarbonate diol, in which at least part of a molecular chainincludes a repeating unit represented by the formula (A) and a repeatingunit represented by the formula (B), while the number average molecularweight is 250 or more and 5,000 or less, and the terminal (A) ratiorepresented by the formula (I) is 1.2 or more and 1.9 or less.[7] The polycarbonate diol according to [6], in which the number averagemolecular weight is 500 or more and 5,000 or less.[8] The polycarbonate diol according to [6] or [7], being obtained byreacting (i) at least one of diols selected from isosorbide, isomannideand isoidide, (ii) a diol having 1 to 15 carbons which may containhetero atom, and (iii) a diester carbonate, by use of atransesterification catalyst.[9] The polycarbonate diol according to [8], in which thetransesterification catalyst is a compound using a metal of Group 1 ormetal of Group 2 on the periodic table.[10] The polycarbonate diol according to [9], in which thetransesterification catalyst is a compound using a metal of Group 2 onthe periodic table.[11] The polycarbonate diol according to any one of [8] to [10], inwhich the highest temperature of the reaction is lower than 180° C.[12] A polycarbonate diol producing method, comprising;

reacting (i) at least one of diols selected from isosorbide, isomannideand isoidide, (ii) a diol having 1 to 15 carbons which may containhetero atom, and (iii) a diester carbonate, by use of atransesterification catalyst, and

in which the highest temperature during the reaction is lower than 180°C.

[13] The polycarbonate diol producing method according to [12], in whichthe transesterification catalyst is a compound using a metal of Group 1or metal of Group 2 on the periodic table.[14] The polycarbonate diol producing method according to [13], thetransesterification catalyst is a compound using a metal of Group 2 onthe periodic table.[15] The polycarbonate diol obtained by the polycarbonate diol producingmethod according to any one of [12] to [14].[16] The polycarbonate diol according to any one of [1] to [5], [8] to[11], and [15], in which the diester carbonate is a diphenyl carbonate.[17] The polycarbonate diol according to any one of [1] to [5], [8] to[11], [15] and [16], in which the content of the diphenyl carbonate is 1weight % or less.[18] The polycarbonate diol according to any one of [1] to [5], [8] to[11], and [15] to [17], in which the diol of the aforementioned (i)contains 20 ppm or less of formic acid.[19] The polycarbonate diol according to any one of [1] to [5], [8] to[11], and [15] to [18], in which 5% or less of molecular chain terminalsare either an alkyloxy group or an aryloxy group among all terminals ofthe molecular chains.[20] The polycarbonate diol according to any one of [1] to [11], and[15] to [19], in which the value of Hazen color number (APHA value:according to JIS K0071-1) is 100 or less.[21] The polycarbonate diol according to any one of [1] to [11] and [15]to [20], in which the molecular weight distribution is 1.5 to 3.5.[22] A polyurethane obtained by using the polycarbonate diol accordingto any one of [1] to [11] and [15] to [21].[23] The polyurethane according to [22], in which by using a strip as asample of the polyurethane having 10 mm in width, 100 mm in length, andabout 50 to 100 μm in thickness, a tensile elongation at break thereofis 400% or less measured under conditions of the distance between chucksof 50 mm, a tensile speed of 500 mm/min., a temperature of 23° C. and arelative humidity of 55%.[24] The polyurethane according to [22] or [23], in which by using astrip as a sample of the polyurethane having 10 mm in width, 100 mm inlength, and about 50 to 100 μm in thickness, a 100% modulus is 10 MPa ormore measured under conditions of the distance between chucks of 50 mm,a tensile speed of 500 mm/min., a temperature of 23° C. and a relativehumidity of 55%.[25] The polyurethane according to any one of [22] to [24], in which byusing a film-like sample of the polyurethane having about 50-100 μm inthickness, a weight reduction ratio is 2% or less at friction testingwith 4.9 N (500 reciprocations) according to JIS L0849.[26] A polyurethane producing method, comprising; reacting thepolycarbonate diol according to any one of [1] to [11] and [15] to [21]and a polyisocyanate thereby obtaining a prepolymer, and reacting theprepolymer with a chain extender.[27] A polyurethane producing method, comprising; mixing thepolycarbonate diol according to any one of [1] to [11] and [15] to [21],a polyisocyanate, and a chain extender at one time, followed by reactingthem.[28] A paint material or a coating agent produced by using thepolyurethane according to any one of [22] to [25].[29] An artificial leather or a synthetic leather produced by using thepolyurethane according to any one of [22] to [25].[30] A water-based polyurethane paint material produced by using thepolyurethane according to any one of [22] to [25].[31] A medical material produced by using the polyurethane according toany one of [22] to [25].[32] An adhesive produced by using the polyurethane according to any oneof [22] to [25].[33] An active-energy radiation curable polymer composition containingan urethane(meth)acrylate oligomer obtained from a raw materialcontaining the polycarbonate diol according to any one of [1] to [11]and [15] to [21], polyisocyanate, and hydroxyalkyl (meth)acrylate.The second aspect of the present invention consists in the following[34] to [44].[34] An active-energy radiation curable polymer composition containingurethane(meth)acrylate oligomer obtained from a raw material containingpolyisocyanate, polycarbonate diol and hydroxyalkyl (meth)acrylate,

in which the polycarbonate diol contains 10 mass % or more of repeatingunit represented by the formula (A), the number average molecular weightof the polycarbonate diol is 500 or more and 5,000 or less, and theaverage number of hydroxyl groups of the polycarbonate diol per onemolecule is 2.2 or less.

[35] The active-energy radiation curable polymer composition accordingto [34], the polycarbonate diol further contains repeating unitrepresented by the formula (B).[36] The active-energy radiation curable polymer composition accordingto [35], X in the formula (B) represents a divalent group having 6carbons.[37] An active-energy radiation curable polymer composition containingurethane(meth)acrylate oligomer obtained from a raw material containingpolyisocyanate, polycarbonate diol and hydroxyalkyl (meth)acrylate,

in which the polycarbonate diol is obtained by reacting (i) at least oneof diols selected from isosorbide, isomannide and isoidide, (ii) diolhaving 1 to 15 carbons which may contain hetero atom, and (iii) diestercarbonate, by use of a transesterification catalyst, and in which thenumber average molecular weight of the polycarbonate diol is 500 or moreand 5,000 or less, and the average number of hydroxyl groups of thepolycarbonate diol per one molecule is 2.2 or less.

[38] The active-energy radiation curable polymer composition accordingto [34] to [37], in which the number average molecular weight of thepolycarbonate diol is 3,000 or less.[39] The active-energy radiation curable polymer composition accordingto any one of [34] to [38], in which the calculated crosslinking pointsmolecular weight is 500 to 10,000.[40] The active-energy radiation curable polymer composition accordingto any one of [34] to [39], in which the raw material further contains ahigh-molecular weight polyol having number average molecular weight ofover 500 excluding the polycarbonate diol.[41] The active-energy radiation curable polymer composition accordingto any one of [34] to [40], in which the raw material further contains alow-molecular weight polyol having number average molecular weight of500 or less excluding the polycarbonate diol.[42] The active-energy radiation curable polymer composition accordingto any one of [34] to [41], in which the urethane(meth)acrylate oligomerhas a structure obtained by an urethane reaction of an urethaneprepolymer having isocyanate group at terminals andhydroxyalkyl(meth)acrylate, and in which the urethane prepolymer isobtained by an urethane reaction of the polyisocyanate and thepolycarbonate diol.[43] A cured film obtained by irradiating the active-energy ray to theactive-energy radiation curable polymer composition according to any oneof [34] to [42].[44] A laminated body having layer composed of the cured film accordingto [43] on a base material.

According to the first aspect of the present invention, a polyurethaneproduced by using a polycarbonate diol is more excellent in degree ofhardness and friction-resistance, compared to a polyurethane made ofpolycarbonate diol derived from a conventionally used 1,6-hexanediol.Therefore the polyurethane is suited for such an application thatresistance is required to physical external factors such as paints,coating agents, adhesive, etc., and this is quite industrially useful.

Also, an active-energy radiation curable polymer composition related tothe second aspect of the present invention contains anurethane(meth)acrylate oligomer having a specific polycarbonate diol asmentioned above, and thus can form a cured film having an excellentcontamination resistance and high degree of hardness.

DESCRIPTION OF THE EMBODIMENTS

Embodiment of the present invention is described in detail below, butthe present invention is not limited to the following embodiments, butit can be applied by changing its form in various ways within the scopeof the invention.

In the present description, (meth)acrylate refers to a collective termfor acrylate and methacrylate, and the term means both of/either theacrylate and/or the methacrylate. This is true to (meth)acryloyl groupand (meth)acrylic acid.

In the present description, “-” means including the values before andafter the symbol as its lowest value and the highest value.

[Polycarbonate Diol]

A polycarbonate diol related to the first aspect of the presentinvention is preferred to be made of a diol and a diester carbonate, andproduced by using a transesterification catalyst. The diol includes atleast one of isosorbide, isomannide and isoidide which are stereoisomersof isosorbide, and isoidide as well as a diol having 1-15 carbons whichmay contain hetero atom. The diester carbonate includes alkyl carbonate,aryl carbonate, and alkylene carbonate, for example.

The transesterification catalyst includes a single metal generallyrecognized having transesterification of esters and a metallic compoundsuch as a hydroxide or a salt of metal. Preferably, a catalyst includingan acetate salt, a carbonate salt, and a hydroxide of a metal of Group 1or 2 on the periodic table, and using a Group 2 metal on the periodictable is more preferred.

A catalyst used during producing may remain in a polycarbonate diol, andit may promote urethane reaction too much, so no catalyst being left ismore preferred. Based on this viewpoint, the amount of catalyst left inthe polycarbonate diol is preferably 100 weight ppm or less whenconverted into a catalyst metal. Any smaller value is preferred as thelower limit of the catalyst remained amount, but 0.1 weight ppm or morecan be specified in terms of simplification of a producing method.

The polycarbonate diol related to the first aspect of the presentinvention is preferred to be a polycarbonate diol including a repeatingunit represented by the following formula (A) in at least part of themolecular chain (hereinafter, a structure represented by the formula (A)may be indicated as “structure (A)”), and having number averagemolecular weight of 250 or more, or more preferably 500 or more and5,000 or less.

The polycarbonate diol related to the first aspect of the presentinvention is preferred to have the Structure (A) in at least part of themolecular chain, and may include other structures. Amount of theaforementioned other structure may be in the range which can exhibit aneffect by those other structures in addition to the effect of thepresent invention, so it can be decided arbitrarily according to thoseother structures.

The aforementioned other structure may have a structure represented bythe following formula (B) (hereinafter, a structure represented by theformula (B) may be referred to as “structure (B)”), for example:

In formula (B), X represents a divalent group having 1 to 15 carbonswhich may contain hetero atom.

{Structural Feature}

The first structural feature of the Structure (A) related to the firstaspect of the present invention is a less-flexible rigid structure withtwo condensed furan rings. Therefore in the polycarbonate diol relatedto the first aspect of the present invention, rigidity appears in thisStructure (A) part. The second feature is an extremely rigid structurewith less freedom in a binding portion of a carbonate group and thecondensed furan rings as well, because the carbonate group is directlybound to the condensed furan rings without a freely rotatable group suchas a methylene group therebetween. The third feature is higherhydrophilic property because two hydrophilic furan rings are placed withhigh-density and therefore affinity with a polar group such as watermolecule is recognized.

The polycarbonate diol related to the first aspect of the presentinvention is preferred that the aforementioned 5% or less of molecularchain terminals are either an alkyloxy group or an aryloxy group amongall terminals of the aforementioned molecular chains and is morepreferred that the aforementioned 5% or less of molecular chainterminals are either an alkyloxy group or an aryloxy group among allterminals of the aforementioned molecular chains and further 95% or moreis a hydroxyl group among both terminals of the molecular chain. In thestructure, this hydroxyl group can react with a polyisocyanate duringpolyurethane forming reaction.

The structure (A) may be continuing in the aforementioned polycarbonatediol, may consist in regular intervals, or may be unevenly distributed.The content of the aforementioned Structure (A) in the aforementionedpolycarbonate diol is 10 mass % or more, preferably 20 mass % or more,and further preferably 40 mass % or more in terms of rigidity,hydrophilic property, etc. Introducing a structure other than thestructure (A) in the molecular chain decreases a melting point andviscosity and results in better handling property because of the poorregularity of polycarbonate diol in addition to effects brought by thepreviously described rigidity and hydrophilic property, etc. Therefore,in the first aspect of the present invention, any structure other thanStructure (A) may be introduced to a polycarbonate diol in the range inwhich effect of the present invention can be obtained.

{Structure (B)}

X in formula (B) representing Structure (B) indicates a divalent grouphaving 1 to 15 carbons which may contain hetero atom, and may include astraight or branched chain or ring group or any of these structures.

The carbon number of elements constituting X is preferably 10 or less,and more preferably 6 or less.

A hetero atom which may be included in X is oxygen atom, sulfur atom,nitrogen atom, etc., while oxygen atom is more preferred in terms ofchemical stability.

A specific example of X group includes a group which is generated byusing a compound exemplified as below as a Structure (B)—giving compoundin producing a polycarbonate diol related to the first aspect of thepresent invention, while more preferred group includes a group obtainedby reacting a preferred compound among the following exemplifiedcompounds.

The Structure (B) may be continuing in the aforementioned polycarbonatediol, may consist in regular intervals, or may be unevenly distributed.The content of the aforementioned Structure (B) in the aforementionedpolycarbonate diol is preferred to consist at 80 mass % or less in termsof poor polycarbonate diol regularity and better handling due todecreased melting point and viscosity, while 60 mass % or less is morepreferred, 40 mass % or less is further preferred, and 20 mass % or lessis specially preferred.

{Ratio of Structure (A) and Structure (B)}

The ratio of Structure (A) and Structure (B) constituting thepolycarbonate diol-molecular chain related to the first aspect of thepresent invention (hereinafter, may be referred as “(A)/(B) ratio”) isusually Structure (A)/Structure (B)=100/0 to 1/99 by mol ratio.Introducing Structure (B) into a molecular chain disarranges thepolycarbonate diol regularity, lowers the melting point and viscosity,and therefore improves handling property. Effects of the presentinvention such as the aforementioned rigidity and hydrophilic property,etc. are mainly introduced by the Structure (A) part, so if the ratio ofStructure (A) part is too small in the polycarbonate diol related to thefirst aspect of the present invention, its effects may not be enough.(A)/(B) ratio of 100/0 to 10/90 is preferred, 80/20 to 20/80 is morepreferred, while 70/30 to 30/70 is further preferred.

In the polycarbonate diol related to the first aspect of the presentinvention, the ratio of Structure (A)/Structure (B) in the molecularchain terminals, which is ratio of a part forming the molecular chainterminals by combining the structured represented by formula (A) andhydrogen atom, or an alkyloxy group or an aryloxy group, and a partforming the molecular chain terminals by combining the structurerepresented by formula (B) and hydrogen atom, or an alkyloxy group or anaryloxy group (hereinafter, this ratio may be referred as “Terminalratio of (A)/(B)”), is preferably 95/5 to 20/80, more preferably 90/10to 30/70, and further preferably 80/20 to 40/60. In this molecular chainterminal, if Structure (B) part is larger than this range, designedfeatures such as hardness may not be obtained.

The ratio of the molecular chain terminal's Structure (A) with the totalnumber of the molecular chain terminal's Structure (A) and (B), as wellas the ratio of Structure (A) in all molecular chains to the totalnumber of Structure (A) and (B) in all molecular chains obtained by thefollowing formula (I) (hereinafter, it may be referred as “Terminal (A)ratio (I)” is not specifically limited, but usually, 1.1 or more,preferably 1.2 or more, more preferably 1.3 or more, and speciallypreferably 1.4 or more, while is usually 5.0 or less, preferably 3.0 orless, more preferably 2.0 or less, further preferably 1.9 or less, andspecially preferably 1.8 or less. When this terminal (A) ratio (I)exceeds the above upper limit, the urethane reaction speed becomes toofast and therefore designed physical property such as hardness may notbe obtained, while it lowers the above lower limit, practically enoughurethane reaction speed may not be obtained for industrial practice. Theterminal (A) ratio (I) may be adjusted by the ratio of diol which is araw material of Structure (A) and (B), types or amount of catalysts, andmaximum temperature and times of reaction.

Terminal (A) ratio (I)={(The number of structure (A) in molecular chainterminal)/(The total number of structures (A) and (B) in molecular chainterminal)}/{(The number of structure (A) in molecular chain)/(The totalnumber of structures (A) and (B) in molecular chain)}  [Mathematicalformula 2]

{Raw Material Monomer}

The polycarbonate diol related to the first aspect of the presentinvention is, as discussed later, is made from raw materials of diol anddiester carbonate.

[Diester Carbonate]

Available diester carbonate is not limited as long as an effect of thepresent invention is exhibited, but includes an alkyl carbonate, an arylcarbonate, or an alkylene carbonate. Among them, adopting the arylcarbonate exhibits an advantage of speedy reaction. On the other hand,phenols having a high boiling point and which are made of the arylcarbonate are obtained as a by-product, but any lower residual volume ofthe phenols in the polycarbonate diol products is preferred. It can be apolymerization inhibitor because of a monofunctional compound and anirritating material.

Specific examples of the dialkyl carbonate, the diaryl carbonate, andthe alkylene carbonate the which are diester carbonates which can beused for producing the polycarbonate diol related to the first aspect ofthe present invention are as follows:

Examples of the dialkyl carbonate includes dimetyl carbonate, diethylcarbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutylcarbonate, ethyl-n-butyl carbonate, and ethyl-isobutyl carbonate, whiledimetyl carbonate and diethyl carbonate are preferred.

Examples of the diaryl carbonate includes diphenyl carbonate, ditolylcarbonate, bis(chlorophenyl) carbonate, di-m-cresyl carbonate, whilediphenyl carbonate is preferred.

Further, alkylene carbonate example includes, ethylene carbonate,trimethylene carbonate, tetramethylene carbonate, 1,2-propylenecarbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylenecarbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate,1,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylenecarbonate, 2,4-pentylene carbonate, and neopentyl carbonate, whileethylene carbonate is preferred.

These may be used by one type alone, or by two or more types together.

Among them, diaryl carbonate is excellent in reaction property andpreferred because of its effectiveness in industrial producing, whilediphenyl carbonate is easily available inexpensively as an industrialraw material, so it is more preferred.

[Diol]

On the other hand, among the diol, followings are specific diol examplesgiving the Structure (A) and (B) included in the polycarbonate diolrelated to the first aspect of the present invention.

(Raw Material Diol of Structure (A))

Specific raw material diol examples giving the Structure (A) includesisosorbide, isomannide and isoidide, which are stereoisomers ofisosorbide, while these may be used by one type alone or by two types ormore together. Among them, the isosorbide is preferred since it iseasily obtained by dehydration of sorbitol and is commercially availableby industrial volume.

(Structure (B) Raw Material Diol)

Specific raw material diol examples giving Structure (B) include theaforementioned diols having 1 to 15 carbons which may contain heteroatom, or preferably the diols having 2 to 10 carbons as follows:

Terminal diols of straight chain hydrocarbons including ethylene glycol,1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexanediol,1,7-heptane diol, 1,8-octane diol, 1,9-nonane diol, 1,10-decane diol,1,11-undecane diol and 1,12-dodecane diol;

Chain diols having ethers including diethylene glycol, triethyleneglycol, tetraethylene glycol, pentaethylene glycol, polyethylene glycol,polypropylene glycol, and polytetramethylene glycol;Thioether diols including bishydroxyethylthioether;Diols having a branched chain including 2-methyl-1,3-propane diol,2-ethyl-1,3-propane diol, 2-butyl-1,3-propane diol,2,2-dimethyl-1,3-propane diol, 2-ethyl-2-butyl-1,3-propane diol,2,2-diethyl-1,3-propane diol, 2-pentyl-2-propyl-1,3-propane diol,3-methyl-1,5-pentane diol, 3,3-dimethyl-1,5-pentane diol,2,2,4,4-tetramethyl-1,5-pentane diol, 2-ethyl-1,6-hexanediol, and2,2,9,9-tetramethyl-1,10-decane diol;Diols having alicyclic structure including 1,3-cyclohexanediol,1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4,4-dicyclohexyldimethylmethane diol, 2,2″-bis(4-hydroxycyclohexyl)propane,1,4-dihydroxyethylcyclohexane, 4,4′-isopropylidenedicyclohexanol, and4,4′-isopropylidenebis(2,2′-hydroxyethoxycyclohexane),norbornane-2,3-dimethanol;Diols having ring group with hetero atoms in its ring including2,5-bis(hydroxymethyl)tetrahydrofuran, 3,4-dihydroxytetrahydrofuran,3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane(cas number: 1455-42-1), and2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-yl)-2-methylpropane-1-ol (casnumber: 59802-10-7);Nitrogen-containing diols including diethanolamine, andN-methyl-diethanolamine;Sulfur-containing diols including bis(hydroxyethyl)sulfide;

Among these diols, more preferable raw material diols in terms ofindustrial availability, excellent physical property regarding theobtained-polycarbonate diol and polyurethane include ethylene glycol,1,3-propanediol, 1,4-butane diol, 1,5-pentane diol, 1,6-hexanediol, and1,7-heptane diol for straight chain carbon terminal diols, whilediethylene glycol, triethylene glycol, tetraethylene glycol,polypropylene glycol, and polytetramethylene glycol for chain diolshaving ether group, while 2-methyl-1,3-propane diol, 2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propane diol, 2-ethyl-2-butyl-1,3-propane diol,2,2-diethyl-1,3-propane diol, 3-methyl-1,5-pentane diol,3,3-dimethyl-1,5-pentane diol, 2,2,4,4-tetramethyl-1,5-pentane diol, and2-ethyl-1,6-hexanediol for diols having branched chains, while1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol,4,4-dicyclohexyl dimethylmethane diol, 2,2′-bis(4-hydroxycyclohexyl)propane, 4,4′-isopropylidenedicyclohexanol, andnorbornane-2,3-dimethanol for diols having alicyclic structure, while3,4-dihydroxytetrahydrofuran,3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane(cas number: 1455-42-1),2-(5-ethyl-5-hydroxymethyl-1,3-dioxane-2-yl)-2-methylpropane-1-ol (casnumber: 59802-10-7) for diols having ring group with hetero atoms in itsring;

These diols may be used by one type alone, or by two or more typestogether.

{Diol for Structure (A)}

The characteristics of the polycarbonate diol related to the firstaspect of the present invention is including Structure (A), while theaforementioned diols giving this Structure (A) (hereinafter, it may bereferred as “Diol for Structure (A)”) may be unstable, and must becareful for saving and usage. For example, isosorbide is graduallyoxidized with oxygen, so for storage and handling during producing, adeoxygenating agent must be used or a nitrogen atmosphere must beprepared to prevent decomposition by oxygen. Also, water must not bemixed in. When isosorbide is oxidized, a decomposition product includinga formic acid is generated. For example, when a polycarbonate diol isproduced by using isosorbide containing the decomposition product, theobtained polycarbonate diol may have colors or its physical propatiesmay be noticeably deteriorated. It also affects polymerization reaction,and a polymer with its target molecular weight may not be obtained.

As a countermeasure against these, an approach described in knowndocuments may be arbitrarily adopted. For example, Japanese patent laidopen 2009-161745 A regulates a preferable amount of formic acids to becontained in a raw material of dihydroxy compound such as isosorbideused for producing a polycarbonate, and describes that using the definedamount or less of dihydroxy compound results in a polycarbonate withbetter physical properties.

This is true for producing the polycarbonate diol related to the firstaspect of the present invention, and the amount of formic acids to becontained in the Diol for Structure (A) is not specifically limited, butits upper limit is usually 20 ppm, preferably 10 ppm, more preferably 5ppm, while the lower limit is 0.1 ppm or preferably 1 ppm.

These diols for Structure (A) generate acid substances such as formicacid when deteriorated due to oxidization, which tends to result inlower pH. Therefore, pH may be used for evaluation as an index foravailable diol for Structure (A). For example, as described in WO09/057609, pH may be measured as an aqueous solution containing 40% ofraw material diol by a pH indicator.

The lower limit of pH of the aqueous solution containing 40% of diol forStructure (A) necessary for producing the polycarbonate diol related tothe first aspect of the present invention is not specifically limited,but is usually pH 3, preferably pH 4, and more preferably pH 5, whileits upper limit is pH 11, and preferably pH 10.

Diol for Structure (A) generates a peroxide by oxidative degradation.Any lower amount of this peroxide is preferred because it may causecoloration in producing a polycarbonate diol or during urethanereaction. The amount of peroxide in diol for Structure (A) relative tothe weight of diol for Structure (A) is usually 10 ppm or less,preferably 5 ppm or less, more preferably 3 ppm or less, and furtherpreferably 1 ppm or less. Its lower limit is not specifically limited,but usually, 0.01 ppm or more.

When diol for Structure (A) contains a metal of Group 1 and/or 2 on theperiodic table, the reaction speed may be influenced during reaction forforming polycarbonate or the polyurethane reaction of the obtainedpolycarbonate diol. Therefore, the content of the metal of Group 1and/or 2 on the periodic table in the diol for Structure (A) is notspecifically limited, but any lower content is preferred, while itsupper limit of the metal weight ratio, relative to weight of diol forStructure (A), is usually 10 ppm, preferably 5 ppm, more preferably 3ppm, further preferably 1 ppm, or specially preferably nothing of themetal of Group 1 and/or 2 on the periodic table.

When a halogen component such as a chloride ion or a bromide ion iscontained in the Diol for Structure (A), it may influence on reactionsor causes coloration during reaction for forming polycarbonate or thepolyurethane reaction of the obtained polycarbonate diol, therefore,smaller content is preferred. Usually, the upper limit of halogencomponent content in diol for Structure (A) is, relative to diol forStructure (A) weight, 10 ppm, preferably 5 ppm, and more preferably 1ppm as halogen content.

The diol for Structure (A) which is deteriorated by oxidation, or whichcontains the above impure substance, can be purified by distillation,etc., for example. Therefore, when the diol is distilled beforepolymerization usage and contains the impurities within the above range,the diol can be used. In order to prevent it from oxidative degradationagain after distillation, adding a stabilization agent is useful. Anyusually and generally used organic compound as antioxidant can be usedwithout limitation as a specific stabilization agent, which includesphenol stabilization agent such as butylhydroxytoluene,butylhydroxyanisole, 2,6-di-t-butyl-4-methylphenol,2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-6-di-t-pentylphenylacrylate(manufactured by Sumitomo Chemical, product name: Sumilizer (registeredtrademark) GS), and a phosphorous stabilization agent such as a6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f] [1,3,2] dioxaphosphepin (manufactured by Sumitomo Chemical,product name: Sumilizer (registered trademark) GP),bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, for example.

{Molecular Weight/Molecular Weight Distribution}

The lower limit of the number average molecular weight (Mn) ofpolycarbonate diol related to the first aspect the present invention isusually 250, preferably 500, more preferably 700, and especiallypreferably 1,000. On the other hand, the upper limit is usually 5,000,preferably 4,000 or more preferably 3,000. When the number averagemolecular weight of polycarbonate diol is lower than the aforementionedlower limit, enough hardness which is a characteristic of the presentinvention may not be obtained after urethanization. On the other hand,when it exceeds the aforementioned upper limit, a problem is pausedduring polyurethanization handling.

The molecular weight distribution of the polycarbonate diol related tothe first aspect of the present invention (Mw/Mn) is not specificallylimited, but its lower limit is usually 1.5, and preferably 2.0. Usuallythe upper limit is 3.5, and preferably 3.0.

When the molecular weight distribution exceeds the above range, thephysical properties of the polyurethane produced by using thispolycarbonate diol tends to be deteriorated such as hardening under lowtemperature, or poor stretching, while trying to produce a polycarbonatediol of which molecular weight distribution is lower than the aboverange, a high-level purification such as excluding oligomer may berequired.

Where, Mw represents the weight-average molecular weight and Mnrepresents the number average molecular weight, which can be usuallyobtained by gel permeation chromatography (GPC) measurement.

{The Proportion of Numbers where Molecular Chain Terminal of thePolycarbonate Diol is Either an Alkyloxy Group or an Aryloxy Group andHydroxy Value Thereof}

The polycarbonate diol related to the first aspect of the presentinvention has basically hydroxyl group for its polymer terminalstructure. However, the polycarbonate diol product obtained by thereaction of a diol and a diester carbonate, may partially include animpurity of which polymer terminal does not have a hydroxyl groupstructure. A specific example of that structure has a molecular chainterminal which is either an alkyloxy group or an aryloxy group, most ofwhich has a structure derived from a diester carbonate.

For example, when a diphenyl carbonate is used as a diester carbonate, aphenoxy group (PhO—) may remain as an aryloxy group, when a dimethylcarbonate is used methoxy group (MeO—) may remain as alkyloxy group,when a diethyl carbonate is used ethoxy group (EtO—) may remain as aterminal group, and when ethylene carbonate is used hydroxyethoxy group(HOCH₂CH₂O—) may remain as a terminal group (where Ph represents aphenyl group, Me represents a methyl group and Et represents an ethylgroup).

In the present invention, the proportion of the structure, in which amolecular chain terminal included in a polycarbonate diol products iseither an alkyloxy group or an aryloxy group, is usually 5 mol % or lessof all terminals as the number of its terminal groups, preferably 3 mol% or less, and more preferably 1 mol % or less. The lower limit of theproportion of numbers where its molecular chain terminal is either analkyloxy group or an aryloxy group is not specifically limited, andusually is 0.01 mol %, preferably 0.001 mol %, and most preferably 0 mol%. When the proportion of alkyloxy or aryloxy group terminals is large,a problem such as degree of polymerization remaining low duringpolyurethanization may occur.

The polycarbonate diol related to the first aspect of the presentinvention is, as discussed above, the proportion of numbers where itsmolecular chain terminal is either an alkyloxy group or an aryloxy groupis usually 5% or less, both terminal groups of the molecular chain arebasically hydroxyl groups, which is the structure where this hydroxylgroup can be reacted with isocyanate during polyurethanization reaction.

The hydroxyl value of the polycarbonate diol related to the first aspectof the present invention is not specifically limited, but the lowerlimit is usually 10 mg-KOH/g, preferably 20 mg-KOH/g, and morepreferably 35 mg-KOH/g. And the upper limit is usually 230 mg-KOH/g,preferably 160 mg-KOH/g, and more preferably 130 mg-KOH/g. When thehydroxyl value is lower than the above lower limit, viscosity of thepolycarbonate diol is too high and its polyurethanization handling maybecome difficult, while it is higher than the above upper limit strengthand hardness of the obtained-polyurethane may not be enough afterpolyurethanization.

{Ether Structure}

The polycarbonate diol related to the first aspect of the presentinvention is based on a structure in which a raw material diol ispolymerized by a carbonate group. However, some producing method maypartially mix an ether structure which is not the aforementionedStructure (A), while when that amount increases, its weather and heatresistance may be deteriorated, so it is preferred that the proportionof non-Structure (A) ether structure is not too large.

In terms of ensuring characteristics such as weather and heat resistanceby reducing the proportion of non-Structure (A) ether structure in thepolycarbonate diol, the ratio of non-Structure (A) ether binding and thecarbonate binding in the polycarbonate diol molecular chains related tothe first aspect of the present invention is not specifically limited,but is usually 2/98 or less by mol ratio, preferably 1/99 or less, andmore preferably 0.5/99.5 or less.

When Structure (B) also contains an ether binding, it is preferred tohave not too large ratio of an ether structure which is neitherStructure (A) nor (B).

In such a case, the ratio of the ether binding which is neitherStructure (A) nor (B) and the carbonate binding in the polycarbonatediol molecular chain related to the first aspect of the presentinvention is not specifically limited, but is usually 2/98 or less bymol ratio, preferably 1/99 or less, and more preferably 0.5/99.5 orless.

{Viscosity/Solvent Dissolution Property}

The polycarbonate diol related to the first aspect of the presentinvention usually shows a property of a liquid-like to wax-like whiteturbidity solid substance around a room temperature, while heating itcan lower its viscosity for better handling. It can also be dissolvedinto amide solvent such as dimethylformamide, dimethylacetamide, estersolvent such as γ-butyrolactone, sulfoxide solvent such as dimethylsulfoxide for easy transportation and better reaction.

The property of the polycarbonate diol related to the first aspect ofthe present invention is as mentioned above a liquid-like to wax-likewhite turbidity solid substance around a room temperature, and itsproperties vary according to a temperature. In terms of viscosity, forexample, the lower limit of the viscosity of the polycarbonate diolrelated to the first aspect of the present invention at 40° C. ispreferably 0.1 Pa·s, more preferably 1 Pa·s, and further preferably 5Pa·s, while the upper limit is preferably 108 Pa·s, more preferably 107Pa·s, and further preferably 106 Pa·s.

{APHA Value}

The color of the polycarbonate diol related to the first aspect of thepresent invention is preferred to be in a range which does not affect apolyurethane color, while its coloration degree is not specificallylimited by Hazen color number (based on JIS K0071-1) (APHA), but ispreferably 100 or less, more preferably 50 or less, and furtherpreferably 30 or less.

{Impurity Content} [Phenols]

The amount of phenols contained in the polycarbonate diol related to thefirst aspect of the present invention is not specifically limited, butthe amount is preferably any smaller, preferably 0.1 weight % or less(hereinafter, “weight %” may be referred as “mass %”), is morepreferably 0.01 weight % or less, and further preferably 0.001 weight %or less. Because phenol is monofunctionalized compound, it can be apolymerization inhibitor during polyurethanization as well as anirritating material.

[Diester Carbonate]

In the polycarbonate diol product related to the first aspect of thepresent invention, a diester carbonate sometimes remain after being usedas a raw material during producing, and the remained amount of thediester carbonate in the polycarbonate diol product related to the firstaspect of the present invention is not limited, but any smaller amountis preferred, while the upper limit is usually 5 weight %, preferably 3weight %, and more preferably 1 weight %. Too many diester carbonatecontent in the polycarbonate diol may obstruct reaction duringpolyurethanization. On the other hand, the lower limit is notspecifically limited, but is 0.1 weight %, preferably 0.01 weight %, andmore preferably 0 weight %.

[Diol]

In the polycarbonate diol related to the first aspect of the presentinvention, a raw material diol may remain after being used forproducing. The remained amount of raw material diol in the polycarbonatediol related to the first aspect of the present invention is notlimited, but any smaller amount is preferred, while it is usually 10weight % or less, preferably 5 weight % or less, more preferably 3weight % or less, or more preferably 1 weight % or less, preferably 0.1weight % or less, and tore preferably 0.05 weight % or less. When atleast one of diols selected from isosorbide, isomannide, or isoidide(hereinafter, to be abbreviated as “isosorbides”) is used, any smalleramount of the isosorbides remaining in the polycarbonate diol ispreferred, while it is usually 10 weight % or less, preferably 5 weight% or less, more preferably 3 weight % or less, further preferably 1weight % or less, specially preferably 0.1 weight % or less, and mostpreferably 0.01 weight % or less. When too much amount of the rawmaterial diol remains in the polycarbonate diol, not enough molecularlength of the soft segment part is obtained after polyurethanization.

The diol which was a raw material of polyurethane diol can be identifiedby NMR measurement of a polycarbonate diol product, NMR measurementand/or GC and LC measurement of unreacted diols contained in theproduct, and if an unreacted product remains, the diester carbonate canbe identified by NMR measurements and/or GC and LC measurements. Inaddition, impurities such as an alcohol component to be made a byproductduring the diester carbonate reaction are identified by NMR measurementsand/or GC and LC measurement of products, which can estimate thestructure of the raw material diester carbonate.

[Transesterification Catalyst]

In producing the polycarbonate diol related to the first aspect of thepresent invention, as described later, a transesterification catalystmay be used as required in order to promote polymerization. In such acase, the catalyst may remain in the obtained polycarbonate diol, but iftoo much catalyst remains, controlling the reaction is difficult duringpolyurethanization reaction, and the polyurethanization reaction isaccelerated more than expected to cause gelation, which may not resultin an uniform polyurethane, so no catalyst remaining is preferred.

The upper limit of remained catalyst amount in the polycarbonate diol isnot specifically limited, but for obtaining a homogeneous polyurethanefrom this polycarbonate diol, the upper limit is usually 100 weight ppmin terms of catalyst metal, preferably 50 weight ppm, more preferably 30weight ppm, and especially preferably 10 weight ppm. A type of remainingmetal includes a catalytic activity component-metal having anesterification reaction ability as mentioned below.

In addition, the lower limit of the catalyst amount remaining in thepolycarbonate diol is not specifically limited, but the lower limit isusually 0.01 weight ppm in terms of catalyst metal, preferably 0.1weight ppm, more preferably 1 weight ppm, and especially preferably 5weight ppm. Removing a catalyst used for producing a polycarbonate diolis usually difficult after producing, and controlling the amount ofremaining catalyst to be lower than the lower limit value of the amountas described later is difficult.

The amount of the aforementioned catalyst in the polycarbonate diol canbe adjusted by the catalyst amount to be used for producing, or catalystisolation by filtering the product, etc. or catalyst extraction using asolvent such as water.

[Cyclic Carbonate]

A polycarbonate diol product may contain a cyclic carbonate which wassubgenerated during producing. For example, when a 1,3-propanediol isapplied as a raw material diol, 1,3-dioxane-2-on or a cyclic carbonateconsisting of two or more molecules of this, etc. may be generated as acyclic compound and contained in the polycarbonate diol. These compoundsare impurities which may cause a side reaction during polyurethanizationreaction, so removing them during producing is preferred.

Content of these cyclic carbonates of impurities contained in thepolycarbonate diol related to the first aspect of the present inventionis not limited, but is usually 3 weight % or less, preferably 1 weight %or less, and more preferably 0.5 weight % or less.

{Urethanization Reaction Speed}

The reaction speed of urethanization reaction of the polycarbonate diolrelated to the first aspect of the present invention can be evaluated asa load value [V] of motor obtained through following steps. The loadvalue [V] of motor is obtained by steps of, making the aforementionedpolycarbonate diol to be an N,N-dimethylformamide solution, adding 0.98times of a diphenylmethane diisocyanate relative to mol equivalentamount of the polycarbonate diol, using the motor as a power source, andagitating it for a specified amount of time by 100 rpm. The lower limitof the motor load in 30 minutes after a diphenylmethane diisocyanate isadded is usually 0.10 V, preferably 0.13 V, more preferably 0.20 V,while the upper limit is usually 2.00 V, preferably 1.95 V, and morepreferably 1.90 V. The lower limit of the motor load in 60 minutes aftera diphenylmethane diisocyanate is added is usually 0.10 V, preferably0.13 V, more preferably 0.20 V, while the upper limit is usually 2.00 V,preferably 1.95 V, and more preferably 1.90 V. If it lowers the abovelower limit, polymerization may not proceed, while it exceeds the aboveupper limit, its molecular weight may be too high or gelation occurs.

Similarly, the lower limit of time (min.) when the motor load valuereaches 0.7 V is usually 8 min., preferably 10 min, and more preferably15 min., while the upper limit is usually 240 min., preferably 200 min.,and more preferably 120 min. Similarly, the lower limit of time (min.)when the motor load value reaches 1.0 V is usually 2 min., preferably 5min, and more preferably 10 min., while the upper limit is usually 120min., preferably 90 min., and more preferably 60 min. If it lowers theabove lower limit, its molecular weight may be too high or gelationoccurs, while it exceeds the above upper limit, polymerization may notproceed.

The motor load value [V] can be measured by extracting the motor valuewhen an N,N-dimethylformamide solution of the polycarbonate diol isagitated at 100 rpm from the motor load value after it is agitated for acertain amount of time by 100 rpm after a diphenylmethane diisocyanateis added. A motor of which rotation range is between 10 to 600 rpm,maximum torque at 600 rpm redline is around 0.49 N-m, its motor loadvalue can be outputted between around 0 and 5 V is used, a 500mL-separable flask is used as a reactor, four wings combining two anchortypes are used as agitation wings, and then measurement is done underthe condition of nitrogen circulation or encapsulation.

{Process of Production}

The polycarbonate diol related to the first aspect of the presentinvention can be produced by transesterification of a raw material diolrepresented by isosorbide giving the aforementioned structure (A), diolssuch as a raw material diol giving the aforementioned structure (B) usedas required and the aforementioned diester carbonate, by using anesterification catalyst as required. For example, it can be obtained byreacting (i) at least one of diols selected from isosorbide, isomannideand isoidide, (ii) diol having 1-15 carbons which may contain heteroatom, and (iii) diester carbonate by use of a transesterificationcatalyst.

The following describes its producing method.

[Transesterification Catalyst]

Any metal which is generally known to have an esterification reactionability may be used without limitation as a metal which can be used as atransesterification catalyst.

Examples of catalyst metals include a metal of Group 1 on the periodictable such as lithium, natrium, potassium, rubidium, and cesium; a metalof Group 2 on the periodic table such as magnesium, calcium, strontium,and barium; a metal of Group 4 on the periodic table such as titanium,zirconium; a metal of Group 5 on the periodic table such as hafnium; ametal of Group 9 on the periodic table such as cobalt; a metal of Group12 on the periodic table such as zinc; a metal of Group 13 on theperiodic table such as aluminum; a metal of Group 14 on the periodictable such as germanium, tin, lead; and a metal of Group 15 on theperiodic table such as antimony, bismuth; and lanthanide metals such aslantern, cerium, europium, and ytterbium. Among them, in terms ofesterification reaction acceleration, a metal of Group 1 on the periodictable, a metal of Group 2 on the periodic table, a metal of Group 4 onthe periodic table, a metal of Group 5 on the periodic table, a metal ofGroup 9 on the periodic table, a metal of Group 12 on the periodictable, a metal of Group 13 on the periodic table, and a metal of Group14 on the periodic table are preferred, while a metal of Group 1 on theperiodic table and a metal of Group 2 on the periodic table are morepreferred, while a metal of Group 2 on the periodic table is furtherpreferred. Among metals of Group 1 on the periodic table, lithium,potassium, and sodium are preferred, lithium and sodium are morepreferred and sodium is further preferred. Among metals of Group 2 onthe periodic table, magnesium, calcium, and barium are preferred,calcium and magnesium are more preferred, and magnesium is furtherpreferred. These metals may be used as a simple metal, or as a metalcompound such as hydroxide or salt thereof. Salt examples when used assalt includes halide salt such as chloride, bromide, and iodide;carboxylate such as acetate, formate, and benzoate; sulfonate such asmethanesulfonic acid, toluenesulfonic acid, and trifluoromethanesulfonicacid; phosphorus-containing salt such as phosphate, hydrogenphosphate,and dihydrogenphosphate; and acetylacetonate salt; etc. A catalyst metalcan be used as alkoxide such as methoxide and ethoxide.

Among them, preferably acetate, nitrate, sulfate, carbonate, phosphate,hydroxide, halide, and alkoxide are used of metals of Group 1 on theperiodic table, metals of Group 2 on the periodic table, metal of Group4 on the periodic table, metals of Group 5 on the periodic table, metalsof Group 9 on the periodic table, metals of Group 12 on the periodictable, metal of Group 13 on the periodic table, and metals of Group 14on the periodic table, while more preferably acetate, carbonate andhydroxide of metals of Group 1 on the periodic table, or metals of Group2 on the periodic table, while further preferably an acetate of metalsof Group 2 on the periodic table.

These metals and metal compounds may be used by one type alone, or bytwo or more types together.

Specific examples of compounds using a Group 1 metal on the periodictable of an a transesterification catalyst includes sodium hydroxide,potassium hydroxide, cesium hydroxide, lithium hydroxide, sodiumhydrogen carbonate, sodium carbonate, potassium carbonate, cesiumcarbonate, lithium carbonate, sodium acetate, potassium acetate, cesiumacetate, lithium acetate, sodium stearate, potassium stearate, cesiumstearate, lithium stearate, sodium boron hydride, sodium phenylborate,sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate,dibasic sodium phosphate, dibasic potassium phosphate, dibasic lithiumphosphate, disodium phenyl phosphate; bisphenol A including disodiumsalt, dipotassium salt, dicesium salt, dilithium salt; phenol sodiumsalt, potassium salt, cesium salt, and lithium salt, etc.

Compound examples using a Group 2 metal on the periodic table includesmagnesium hydroxide, calcium hydroxide, strontium hydroxide, bariumhydroxide, magnesium hydrogen carbonate, calcium hydrogen carbonate,strontium hydrogen carbonate, barium hydrogen carbonate, magnesiumcarbonate, calcium carbonate, strontium carbonate, barium carbonate,magnesium acetate, calcium acetate, strontium acetate, barium acetate,magnesium stearate, calcium stearate, calcium benzoate, and magnesiumphenylphosphate.

Compound examples using a Group 4 metal on the periodic table, a Group12 metal on the periodic table and a Group 14 metal on the periodictable includes titaniumalkoxide such as tetraethyltitanate,tetraisopropyltitanate, and tetra-n-butyltitanate; titanium halide suchas titanium tetrachloride; zinc salt such as zinc acetate, zincbenzoate, and zinc 2-ethylhexanoate; tin compound such as tinchloride(II), tin chloride(IV), tin acetate(II), tin acetate(IV),dibutyltin dilaurate, dibutyltin oxide, and dibutyltin dimethoxide;zirconium compound such as zirconium acetylacetonato, zirconiumoxyacetate, and zirconium tetrabutoxide; and lead compound such as leadacetate(II), lead acetate(IV), and lead chloride(IV).

[Use Proportion of Raw Materials]

For producing the polycarbonate diol related to the first aspect of thepresent invention, the use amount of diester carbonate is notspecifically limited, but usually by the mol ratio to a total 1 mol ofdiols the lower limit is preferably 0.50, more preferably 0.70, furtherpreferably 0.80, more and more preferably 0.90, especially preferably0.95, and the most preferably 0.98, while the upper limit is usually1.20, preferably 1.15, and more preferably 1.10. If the amount ofdiester carbonate exceeds the aforementioned upper limit, terminal groupof the polycarbonate diol to be obtained tends not to be a hydroxylgroup and the ratio of groups other than hydroxyl group may beincreased, or the molecular weight does not reach the predefined rangeand the polycarbonate diol related to the first aspect of the presentinvention cannot be produced, and if the amount of diester carbonate islower than the aforementioned lower limit, polymerization may not beprocessed to a predefined molecular weight.

In producing the polycarbonate diol related to the first aspect of thepresent invention, the ratio of the amount of the raw material diolgiving Structure (A) and the amount of the raw material diol givingStructure (B) (hereinafter, it may be referred as “Raw material (A)/Rawmaterial (B) ratio) is usually, by mol ratio, Raw material diol givingStructure (A)/Raw material giving Structure (B)=100/0 to 1/99.Introducing Structure (B) into a molecular chain disarranges thepolycarbonate diol regularity, lowers the melting point and viscosity,and therefore improves handling property. Effects of the presentinvention such as the aforementioned rigidity and hydrophilicproperties, etc. are mainly introduced by the Structure (A) part, so ifthe ratio of Structure (A) part is too small in the polycarbonate diolrelated to the first aspect of the present invention, its effects maynot be obtained enough. Raw material (A)/raw material (B) ratio ispreferably 100/0 to 10/90, more preferably 80/20 to 20/80, and furtherpreferably 70/30 to 30/70.

When a transesterification catalyst is used for producing thepolycarbonate diol related to the first aspect of the present invention,an amount to be used is preferably the amount which does not affect aperformance if it remains in the obtained polycarbonate diol, while theweight ratio in terms of metal to the weight of a raw material diol asits upper limit is preferably 500 ppm, more preferably 100 ppm, andfurther preferably 50 ppm. On the other hand, the lower limit must be anamount which can exhibit enough polymerization activity, and preferably0.01 ppm, more preferably 0.1 ppm, and further preferably 1 ppm.

[Reaction Conditions, Etc.]

How to prepare a reaction raw material is not specifically limited, andcan be arbitrarily selected from various kinds of approaches; anapproach of preparing all amounts of a diol, a carbonate ester, and acatalyst altogether for reaction, an approach of firstly preparing thecarbonate ester if the carbonate ester is a solid, heating for melting,and then adding the diol and the catalyst, an approach of firstlypreparing the diol for melting conversely, and then adding the carbonateester and the catalyst, and an approach of reacting a part of the dioland a carbonate ester or a chlorocarbonic ester to synthesize acarbonate diester derivative of the diol, and then reacting it withremaining diol. In the polycarbonate diol related to the first aspect ofthe present invention, to make the ratio of molecular chain terminalwhich is either an alkyloxy group or an aryloxy group to be 5% or less,an approach of adding a part of the diol to be used at the end of itsreaction is also possible. In that case, the upper limit of the diolamount to be added at the end is usually 20% of the diol amount to beprepared, preferably 15%, and more preferably 10%, while the lower limitis 0.1%, preferably 0.5%, and more preferably 1.0%.

Reaction temperature during esterification reaction may be arbitrarilyadopted as long as practicable reaction speed can be obtained at thetemperature. The temperature is not specifically limited, but is usually70° C. or higher, preferably 100° C. or higher, and more preferably 130°C. or higher. The temperature is usually 250° C. or lower, preferably230° C. or lower, more preferably 200° C. or lower, further preferablylower than 180° C., especially preferably 170° C. or lower, and the mostpreferably 165° C. or lower. When the temperature exceeds theaforementioned upper limit, the obtained polycarbonate diol may becolored, an ether structure is generated, the aforementioned terminal(A) ratio (I) may become too large, therefore, in producing thepolyurethane with the raw material of polycarbonate diol, a qualityproblem such as insufficient occurrence of a desired physical propertiesmay be caused.

The reaction can be conducted under a normal pressure, but theesterification reaction is an equilibrated reaction, and distilling awaya low boiling fraction to be generated to outside of a system can biasthe reaction to a generation system. Consequently, it is preferred toadopt a reduced pressure condition for the latter half of the reactionto process the reaction while distilling the low boiling fraction away.Or, in the middle of the reaction, reducing the pressure gradually todistill away the low boiling fraction to be generated and processing thereaction is also possible.

Especially at the final period of the reaction, increasing the degree ofreduced pressure to process the reaction can distill away a byproductsuch as a monoalcohol, phenol, and further a cyclic carbonate, etc.,which is preferred.

The reaction pressure at the end of this reaction is not specificallylimited, but the upper limit is usually 10 kPa, preferably 5 kPa, andmore preferably 1 kPa. In order to effectively distill away these lowboiling fractions, an inert gas such as nitrogen, argon, and helium,etc. can be sent to its reaction system little by little to process thereaction.

When carbonate ester and/or diol having low-boiling point is used foresterification reaction, an approach, in which the reaction is to beconducted near the boiling point of the carbonate ester and/or the diolat its early reaction period, while the temperature is graduallyincreased as the reaction progresses for further reaction progress, isalso adoptable. This case is preferable because distilling of unreactedcarbonate ester can be blocked at the early reaction period. In order toprevent a raw material from being distilled at early reaction period, areflux pipe can be attached to a reactor vessel to process the reactionwhile refluxing the carbonate ester and the diol. In this case, it ispreferred that the prepared raw materials are not lost and its reagentamount ratio can be accurately adjusted.

Polymerization reaction is to be conducted while measuring the molecularweight of polycarbonate diol to be generated, and stops when thepolycarbonate diol reaches the target molecular weight. The reactiontime necessary for polymerization varies substantially, depending on adiol to be used, a carbonate ester, whether a catalyst is used or not,and its type, so it cannot be generalized, but the reaction timenecessary for reaching the desired molecular weight is usually 50 hoursor less, preferably 20 hours or less, and further preferably 10 hours orless.

As mentioned earlier, when a catalyst is used for polymerizationreaction, the catalyst usually remains in the obtained polycarbonatediol, and when a metal catalyst remains, the reaction may not becontrolled during polyurethanization reaction. In order to control thisremaining catalyst influence, a phosphorous compound, for example,having the nearly-equal mols as the used transesterification catalystmay be added. Heating after the addition, as described below, canefficiently inactivate a transesterification catalyst.

A phosphorous compound to be used for inactivation of thetransesterification catalyst includes, inorganic phosphoric acid such asphosphoric acid and phosphorous acid and organic phosphoric acid estersuch as dibutyl phosphate, tributyl phosphate, trioctyl phosphate,triphenyl phosphate, and triphenyl phosphite, for example.

These may be used by one type alone, or by two or more types together.

The amount of the aforementioned phosphorous compound is notspecifically limited, but as described above, the nearly-equivalent molsas the used transesterification catalyst is required, specifically,relative to 1 mols of the used transesterification catalyst, the upperlimit is preferably 5 mols, and more preferably 2 mols, while the lowerlimit is preferably 0.8 mols and more preferably 1.0 mols. When anysmaller amount of phosphorous compound is used, the inactivation of thetransesterification catalyst is not enough in the aforementionedreaction product, and when the obtained polycarbonate diol is used as araw material in producing a polyurethane, for example, reactivity of thepolycarbonate diol to the isocyanate group may not be reduced enough.When a phosphorous compound exceeding this range is used, the obtainedpolycarbonate diol may be colored.

The inactivation of transesterification catalyst can be conducted byadding a phosphorous compound at room temperature, but heating processfurther improves the result. The temperature for this heating process isnot specifically limited, but the upper limit is preferably 150° C.,more preferably 120° C., and further preferably 100° C., while the lowerlimit is preferably 50° C., more preferably 60° C., and furtherpreferably 70° C. If the temperature is lower than the lower limit, ittakes long time to inactivate the transesterification catalystinefficiently, and the degree of inactivation may not be enough. On theother hand, at the temperature over 150° C., the obtained polycarbonatediol may be colored.

The reaction time with a phosphorous compound is not specificallylimited, but is usually 1 to 5 hours.

[Purification]

After the reaction, purification can be conducted in order to remove animpurity of which terminal structure is an alkyloxy group, an impuritywhich is an aryloxy group, phenols, a raw material diol, a carbonateester, a cyclic carbonate byproduct having low-boiling point, and anadded catalyst, etc. For those purification, a distilling approach canbe adopted to remove a low boiling compound. As a specific distillingapproach, like vacuum distillation, hydrodistillation, and thin-filmevaporation, its embodiment is not limited, but an arbitrary approachcan be adopted. In order to remove water-soluble impurities, water,alkaline water, acid water, and chelating agent dissolved solution, etc.may be used for cleaning. In that case, a compound to be dissolved intowater can be arbitrarily selected.

[Polyurethane]

The polycarbonate related to the first aspect of the present inventionis obtained by using the polycarbonate diol related to the first aspectof the above present invention.

An approach for producing the polyurethane related to the first aspectof the present invention by using the polycarbonate diol related to thefirst aspect of the present invention usually adopts a knownpolyurethanization reaction condition for producing the polyurethane.

For example, reacting the polycarbonate diol related to the first aspectof the present invention with polyisocyanate and a chain extender in therange of a room temperature to 200° C. to produce the polyurethanerelated to the first aspect of the present invention. Also, firstlyreacting the polycarbonate diol related to the first aspect of thepresent invention with an excess of polyisocyanate to produce aprepolymer having terminal isocyanate, and increase the polymerizationdegree by using the chain extender to produce the polyurethane.

{Reactive Reagent, Etc.} [Polyisocyanate]

A polyisocyanate used for producing the polyurethane by using thepolycarbonate diol related to the first aspect of the present inventionincludes various kinds of known polyisocyanate compounds such as fattyseries, alicyclic series, and aromatic series.

For example, fatty series diisocyanate such as tetramethylenediisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylenediisocyanate, 2,4,4-trimethyl hexamethylene diisocyanate,lysinediisocyanate and dimerdiisocyanate which is obtained by convertingcarboxyl group of dimer acid into isocyanate group; alicyclicdiisocyanate such as 1,4-cyclohexanediisocyanate, isophoronediisocyanate, 1-methyl-2,4-cyclohexanediisocyanate,1-methyl-2,6-cyclohexanediisocyanate,4,4′-dicyclohexylmethanediisocyanate and1,3-bis(isocyanatemethyl)cyclohexane; and aromatic diisocyanate such asa xylylene diisocyanate, 4,4′-diphenyldiisocyanate,2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate,m-phenylenediisocyanate, p-phenylenediisocyanate, 4,4′-diphenylmethanediisocyanate, 4,4′-diphenyldimethylmethanediisocyanate, 4,4′-dibenzyldiisocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,5-naphthylene diisocyanate,3,3′-dimethyl-4,4′-biphenylene diisocyanate, polymethylenepolyphenylisocyanate, phenylenediisocyanate and m-tetramethylxylylenediisocyanate. These may be used by one type alone, or by two or moretypes together.

Among them, the most preferable organic diisocyanate is the4,4′-diphenylmethane diisocyanate, the hexamethylene diisocyanate andthe isophorone diisocyanate because the physical properties balance ofthe polyurethane to be obtained is preferable and these compounds can beeasily and inexpensively obtained with high volume in terms ofindustrial view point.

[Chain Extender]

The chain extender to be used for producing the polyurethane related tothe first aspect of the present invention is a low-molecular weightcompound having at least two active hydrogens which react withisocyanate group, and usually is exemplified by polyol and polyamine.

Specific examples of these include straight chain diols such as ethyleneglycol, diethylene glycol, 1,3-propylene glycol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 2,4-heptanediol, 1,8-octanediol,1,4-dimethylol hexane, 1,9-nonanediol, and 1,12-dodecanediol, dimerdiol;diols having branched chains such as 2-methyl-1,3-propanediol,2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,2-methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol,2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, and2-butyl-2-ethyl-1,3-propanediol; diols having a ring group such as1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and1,4-dihydroxyethylcyclohexane; diols having aromatic group such asxylylene glycol, 1,4-dihydroxyethyl benzene, and4,4′-methylenebis(hydroxyethyl benzene; polyols such as glycerin,trimethylolpropane, and pentaerythritol; hydroxy amine such asN-methylethanolamine, and N-ethylethanolamine; polyamine such asethylene diamine, 1,3-propane diamine, hexamethylenediamine,triethylenetetramine, diethylene triamine, isophoronediamine,4,4′-diaminodicyclohexylmetane, 2-hydroxyethylpropylene diamine,di-2-hydroxyethylethylene diamine, di-2-hydroxyethylpropylene diamine,2-hydroxypropylethylene diamine, di-2-hydroxypropylethylene diamine,4,4′-diphenylmethanediamine, methylenebis(o-chloroaniline),xylylenediamine, diphenyldiamine, tolylenediamine, hydrazine,piperazine, and N,N′-diaminopiperazine; and water.

These chain extenders may be used by one type alone, or by two or moretypes together.

The most preferable chain extender among them includes 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol,1,4-cyclohexanedimethanol, 1,4-dihydroxyethylcyclohexane, ethylenediamine, and 1,3-propane diamine, because the physical propertiesbalance of the polyurethane to be obtained is preferable and thesecompounds can be easily and inexpensively obtained with high volume interms of industrial view point.

[Chain Terminator]

In producing the polyurethane related to the first aspect of the presentinvention, in order to control the obtained polyurethane molecularweight, a chain terminator having one active hydrogen group may be usedas required.

Examples of these chain terminators include aliphatic mono-ols havinghydroxyl group such as ethanol, propanol, butanol, and hexanol, andaliphatic mono-amines having amino group such as diethylamine,dibutylamine, n-butylamine, monoethanolamine, and diethanolamine.

These may be used by one type alone, or by two or more types together.

[Catalyst]

In a polyurethane forming reaction for producing the polyurethanerelated to the first aspect of the present invention, an amine seriescatalyst such as triethylamine, N-ethylmorpholine, triethylene diamine,or tin compound such as tin series catalyst such as trimethyltin laurateor dibutyltin dilaurate, further a known urethane polymerizationcatalyst that is typified by organic metallic salt such as titaniumseries compound. The urethane polymerization catalyst may be used by onetype alone, or by two or more types together.

[Other Polyol]

In producing the polyurethane related to the first aspect of the presentinvention, in addition to the polycarbonate diol related to the firstaspect of the present invention, other known polyol may be usedtogether, as required. Examples of those available known polyolsinclude, polyoxyalkylene glycols such as polyethylene glycol,polypropylene glycol, and polyoxytetramethylene glycol (PTMG); alkyleneoxide adduct of polyalchol such as ethylene oxide adduct and propyleneoxide adduct of bisphenol A and glycerin; polyesterpolyol,polycaprolactonepolyol, and polycarbonatepolyol.

Examples of polyesterpolyol include a diacid such as adipic acid,phthalic acid, isophthalic acid, maleic acid, succinic acid, and fumaricacid, glycol series such as ethylene glycol, diethylene glycol,1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,and trimethylolpropane.

Available polycarbonate polyol examples include a homopolycarbonate dioland a copolymerized polycarbonate diol which are produced from1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanedimethanol,and 2-methylpropanediol.

When other polyols are used, in order to obtain enough effects of usingthe polycarbonate diol related to the first aspect of the presentinvention, the proportion of the polycarbonate diol related to the firstaspect of the present invention among all polyols is not specificallylimited, but is usually 30 weight % or more, especially 50 weight % ormore is preferred.

[Solvent]

A solvent may be used for a polyurethane forming reaction for producingthe polyurethane related to the first aspect of the present invention.

Preferable solvents include amide series solvent such asdimethylformamide, diethylformamide, dimethylacetamide, andN-methylpyrolidone; sulfoxide series solvent such as dimethyl sulfoxide;ether series solvent such as tetrahydrofuran, and dioxane; ketone seriessolvent such as methylisobutylketone, methylethylketone, andcyclohexanone; ester series solvent such as methyl acetate, ethylacetate, and butyl acetate; and aromatic hydrocarbons solvent such astoluene and xylene. These solvents may be used by one type alone, or bya combined solvent of two types or more.

Preferable organic solvents among them are methylethylketone, ethylacetate, toluene, dimethylformamide, dimethylacetamide,N-methylpyrolidone and dimethyl sulfoxide.

By using a polyurethane resin composition containing the polycarbonatediol related to the first aspect of the present invention,polydiisocyanate, and the aforementioned chain extender, a polyurethaneresin of an aqueous dispersion can be produced.

{Process of Production}

As an approach for producing the polyurethane related to the firstaspect of the present invention by using the above mentioned reactionreagent, all general producing methods used for experimentally orindustrially can be adopted.

Examples of them include a method for mixing and reacting a polyolincluding the polycarbonate diol related to the first aspect of thepresent invention, a polyisocyanate, and a chain extender altogether(hereinafter, to be referred as “one-step method”) and a method forfirstly reacting a polyol including the polycarbonate diol related tothe first aspect of the present invention and a polyisocyanate toarrange a prepolymer having isocyanate group at both terminals thereof,and then reacting the prepolymer with a chain extender (hereinafter, tobe referred as “two-step method”).

The two-step method goes through a process that prepares intermediateshaving isocyanate at both of terminals that are corresponding to apolyurethane soft segment, and the process is conducted in advance byreaction of a polyol containing the polycarbonate diol related to thefirst aspect of the present invention with an organic polyisocyanate ofone equivalent or more. Reacting a prepolymer with a chain extenderafter an arrangement is done may enhance the molecular weightarrangement of the soft segment part, which is useful to ensure a phaseseparation of a soft segment from a hard segment.

[One-Step Method]

One-step method is also called one-shot method, which is a method forpreparing a polyol containing the polycarbonate diol related to thefirst aspect of the present invention, a polyisocyanate, and a chainextender altogether for reaction.

The amount of polyisocyanate at the one-step method is not specificallylimited, but when the total of the number of hydroxyl groups of polyolcontaining the polycarbonate diol related to the first aspect of thepresent invention, the number of hydroxyl groups and amino groups ofchain extender are regarded as 1 equivalent weight, and the lower limitis usually 0.7 equivalent weight, preferably 0.8 equivalent weight, morepreferably 0.9 equivalent weight, and especially preferably 0.95equivalent weight, while the upper limit is usually 3.0 equivalentweight, preferably 2.0 equivalent weight, more preferably 1.5 equivalentweight, and further preferably 1.1 equivalent weight.

When the polyisocyanate amount is too large, unreacted isocyanate groupsmay cause side reaction, and desired physical properties may not beobtained, while when it is too small, the molecular weight of thepolyurethane does not become large enough and the desired performancemay not develop.

The amount of the chain extender is not specifically limited, but whenthe number of isocyanates of a polyisocyanate is subtracted f rom thenumber hydroxyl groups of polyol containing the polycarbonate diolrelated to the first aspect of the present invention and thesubtracted-number is regarded as 1 equivalent weight, the lower limit isusually 0.7 equivalent weight, preferably 0.8 equivalent weight, morepreferably 0.9 equivalent weight, and especially preferably 0.95equivalent weight, while the upper limit is 3.0 equivalent weight,preferably 2.0 equivalent weight, more preferably 1.5 equivalent weight,especially preferably 1.1 equivalent weight. When the chain extenderamount is too large, the obtained polyurethane is least soluble to asolvent and processing tends to be difficult, while when it is toosmall, the obtained polyurethane becomes too soft to exhibit enoughstrength, hardness, and an elastic recovery performance and/or anelastic retention capacity cannot be obtained, and the high-temperatureproperty may be deteriorated.

[Two-Step Method]

The two-step method is also called a prepolymer method, comprising;reacting a polyisocyanate and a polyol containing the polycarbonate diolrelated to the first aspect of the present invention in advance by thepolyisocyanate/polyol reaction equivalent weight ratio 1.0 to 10.00 toproduce a prepolymer having isocyanate group at terminals thereof, andthen adding a chain extender having an active hydrogen such as apolyalcohol and an amine compound to produce a polyurethane.

The two-step method can be adopted without a solvent or with a solventtogether.

The polyurethane can be produced by the two-step method by eitherapproach of the following (1) to (3);

(1) Without using a solvent, a polyisocyanate is directly reacted with apolyol containing a polycarbonate diol to produce a prepolymer and usedfor the following chain extension reaction as is.(2) A prepolymer is produced by the (1) approach, solved into a solvent,and then used for the following chain extension reaction.(3) A solvent is adopted from the first time to react polyisocyanate andpolyol containing a polycarbonate diol, and then chain extensionreaction is conducted in the solvent.

In the case of approach (1), it is important to obtain the polyurethaneso that it can coexist with a solvent for activating the chain extenderby an approach of solving the chain extender into a solvent, orintroducing a prepolymer and the chain extender into the solventtogether, etc.

The amount of a polyisocyanate at the two-step method is notspecifically limited, but when the number of hydroxyl groups of a polyolcontaining the polycarbonate diol is regarded as 1 equivalent weight,the lower limit of the number of isocyanates is usually 1.0, andpreferably 1.05, while the upper limit is usually 10.0, preferably 5.0,and more preferably 3.0.

When the amount of this isocyanate is too large, the excessiveisocyanate groups may cause a side reaction to cause unpreferableinfluence on the polyurethane physical properties, while when it is toosmall the molecular weight of the obtained polyurethane may not increaseenough and may cause a problem in strength and/or thermal stability.

The amount of the chain extender is not specifically limited, butrelative to the equivalent amount of the isocyanate group contained inthe prepolymer, the lower limit is usually 0.1, preferably 0.5, and morepreferably 0.8, while the upper limit is usually 5.0, preferably 3.0,and more preferably 2.0.

During the above chain extension reaction, one functionality organicamine and alcohol can coexist in order to adjust the molecular weight.

During the chain extension reaction, each component is reacted withinthe range of 0 to 250° C., but this temperature varies, depending on theamount of a solvent, reactive properties of raw materials to be used,and/or reaction equipment, etc., and is not specifically limited. Whenthe temperature is too low, the reaction speed is too slow and/orproductivity may be deteriorated due to low solubility of raw materialsand polymer substances, while when the temperature is too high, a sideeffect may occur or the obtained polyurethane may be decomposed. Thechain extension reaction may be conducted under reduced pressure whiledegassing.

A catalyst or a stabilizer, etc. may be added for the chain extensionreaction, as required.

Examples of catalysts include one or two types of triethylamine,tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid,phosphoric acid, sulfuric acid, hydrochloric acid, and sulfonic acid,while examples of stabilizers include one or two types of2,6-dibutyl-4-methylphenol, distearyl thiodipropionate,di-beta-naphthyl-phenylenediamine, and tri (dinonylphenyl)phosphite.However, when a chain extender with high reactivity such as short-chainfatty series amine is used, the reaction is preferred to be conductedwithout adding a catalyst.

[Water-Based Polyurethane Emulsion]

A water-based polyurethane emulsion can be produced by using thepolycarbonate diol related to the first aspect of the present invention.

In this case, in producing a prepolymer by reacting a polyol containinga polycarbonate diol and a polyisocyanate, the prepolymer is obtained bymixing a compound having at least one hydrophilic functional group andat least two isocyanate reactive groups, and a polyurethane emulsion isobtained by reacting the obtained-prepolymer with a chain extender.

Here, a hydrophilic functional group of a compound having at least onehydrophilic functional group and at least two isocyanate reactive groupsincludes carboxylic acid group and sulfonic acid group, for example,which is neutralizable with alkaline group. Also, isocyanate reactivegroup means a group of forming urethane bond and urea bond by generallyreacting with isocyanate such as hydroxyl group, primary amino group,and secondary amino group, etc., which are permitted to co-exist withinthe same molecule.

Examples of compound having at least one hydrophilic functional groupand at least two isocyanate reactive groups specifically include2,2′-dimethylol propionic acid, 2,2-methylolbutyric acid, and2,2′-dimethylolvaleric acid. Further, diaminocarboxylic acid, forexample lysine, cystine, and 3,5-diaminocarboxylic acid are exemplified.These may be used by one type alone, or by two or more types together.When these are actually used, they can be neutralized by alkalinecompound such as amine including trimethyl amine, triethylamine,tri-n-propylamine, tributylamine, and triethanolamine, as well as sodiumhydroxide, calcium hydroxide, and ammonia.

In producing the water-based polyurethane emulsion, as for the amount ofa compound having at least one hydrophilic functional group and at leasttwo isocyanate reactive groups, in order to raise dispersion performanceagainst water, the lower limit is, relative to the weight of a polyolcontaining the polycarbonate diol related to the first aspect of thepresent invention, usually 1 weight %, preferably 5 weight %, and morepreferably 10 weight %. On the other hand, if an excess amount is added,the characteristics of the polycarbonate diol related to the firstaspect of the present invention may not be sustained, so the upper limitis usually 50 weight %, preferably 40 weight %, and more preferably 30weight %.

For synthesizing or saving the water-based polyurethane emulsion, ananionic surfactant represented by higher fatty acid, resin acid, acidicfatty alcohol, sulfate ester, higher alkyl sulfonate, alkyl arylsulfonate, sulfonated ricinus, sulfosuccinate ester, etc., cationicsurfactant such as primary amine salt, secondary amine salt, tertiaryamine salt, quaternary amine salt, and pyridinium salt or non-ionicsurfactant, etc. represented by a known reaction product of ethyleneoxide and long-chain fatty alcohol or phenols may be used together tomaintain its emulsion stability.

When the polyurethane emulsion is made by reacting a prepolymer with achain extender, the prepolymer may be neutralized as required anddispersed into water.

These created water-based polyurethane emulsion can be used for variouskinds of application. In particular, a chemical raw material with asmaller environmental load is sought these days, a substitute for aconventional product is possible in order not to use an organic solvent.

Specific suited applications for the water-based polyurethane emulsionincludes a coating agent, a water-based paint, an adhesive agent, asynthetic leather, and an artificial leather, for example. Inparticular, the water-based polyurethane emulsion produced by using thepolycarbonate diol related to the first aspect of the present inventionhas structure (A) in the polycarbonate diol, therefore it is moresuitable as a coating agent. etc. than the water-based polyurethaneemulsion using the conventional polycarbonate diol because of its highhardness, high abrasion resistance, and long-term maintenance of thesurface properties.

Also by using the polycarbonate diol related to the first aspect of thepresent invention, it is possible to react it with polyisocyanate, andthen react with an acrylic acid ester or a methacrylate ester having ahydroxy group, to induce to urethane acrylate, or urethane methacrylate.The urethane acrylate and urethane methacrylate are widely used as acoating agent, its application is not specifically limited, and thepolycarbonate diol related to the first aspect of the present inventioncan be used as a raw material. Furthermore, it can be used by convertinga polymerized functional group from (meth)acrylate to glycidyl group,allyl group, or propargyl group.

{Additives}

To the polyurethane related to the first aspect of the present inventionwhich was produced by using the polycarbonate diol related to the firstaspect of the present invention, an addition agent such as a thermalstabilizer, a light stabilizer, a coloring agent, a bulking agent, astabilizer, an ultraviolet absorber, an oxidation inhibitor, ananti-adhesive agent, a flame retardant, an age inhibitor, and aninorganic filler can be added and mixed as far as characteristics of thepolyurethane related to the first aspect of the present invention is notdamaged.

Compounds available as a thermal stabilizer include phosphorous compoundsuch as phosphoric acid, phosphorous acid's fatty series, aromaticseries or an alkyl group substituted aromatic series ester orhypophosphorous acid derivative, phenylphosphonic acid, phenylphosphineacid, diphenylphosphonic acid, polyphosphonate, dialkyl pentaerythritoldiphosphite, dialkyl bisphenol-A-diphosphite; phenol-based derivative,in particular, hindered phenol compound; sulfur-containing compound suchas thioether-based, dithioic acid salt-based,mercaptobenzimidazole-based, thiocarbanilide-based, thiodipropionic acidester-based; tin-based compound such as tin maleate, and dibutyltinmonoxide.

Specific examples of a hindered phenol compound include Irganox 1010(product name: made by Ciba-Geigy K.K), Irganox 1520 (product name: madeby Ciba-Geigy K.K), etc.

Examples of a phosphorous compound include PEP-36, PEP-24 G, HP-10 (allof these are product names; made by ADEKA Corporation), Irgafos 168(product name: made by Ciba-Geigy K.K), etc. Specific examples ofsulfur-containing compounds include a thioether compound such as adilauryl thiodipropionate (DLTP), or a distearyl thiodipropionate(DSTP).

Examples of available light stabilizers include a benzotriazole-based,and a benzophenone-based compound, etc., and specifically “TINUVIN 622LD”, “TINUVIN 765” (both are made by Ciba Specialty Corp), “SANOLLS-2626”, “SANOL LS-765) (both are made by Sankyosha Co., Ltd.), etc.

Examples of an ultraviolet absorber include “TINUVIN 328”, “TINUVIN234”(both are made by Ciba Specialty Corp), etc.

Examples of a coloring agent include a dye such as a direct dye, an aciddye, a basic dye, and a metal complex dyestuff; an inorganic pigmentsuch as carbon black, titanium oxide, zinc oxide, iron oxide and mica;and an organic pigment such as coupling azo-based, condensed azo-based,anthraquinone-based, thioindigo-based, dioxazon-based, andphthalocyanine-based, etc.

Examples of an inorganic filler include a short glass fiber, a carbonfiber, an alumina, a talc, a graphite, a melamine, and a white clay.

Examples of a flame retardant include an organic compound containing aphosphorus and a halogen, an organic compound containing bromine orchlorine, and an additive and reactive flame retardant such as ammoniumpolyphosphate, aluminum hydroxide, and antimony oxide.

These addition agents may be used by itself alone, or two or more typescan be arbitrarily combined by an arbitrary ratio.

The lower limit of the additive amount of these addition agents is, tothe polyurethane, preferably 0.01 weight %, more preferably 0.05 weight%, and further preferably 0.1 weight %, while the upper limit ispreferably 10 weight %, more preferably 5 weight %, and furtherpreferably 1 weight %. When the additive amount of the addition agent istoo small, the addition effect cannot be enough, while when it is toolarge, precipitation or turbidity may occur in the polyurethane.

{Polyurethane Film/Polyurethane Plate}

In producing a film by using the polyurethane related to the firstaspect of the present invention, the lower limit of the film thicknessis usually 10 μm, preferably 20 μm, and more preferably 30 μm, while theupper limit is usually 1,000 μm, preferably 500 μm, and more preferably100 μm.

When the film is too thick, enough moisture permeability may not beobtained, while it is too thin, its handling may become difficultbecause a pin hole is easily generated and/or the film may be blocked.

The polyurethane film related to the first aspect of the presentinvention is preferred to be used as a medical material such as amedical self-adhesive film, a sanitary material, a packing material, adecoration film, and any other moisture permeability material, etc. Thepolyurethane film related to the first aspect of the present inventionmay be the film which was formed on a base such as a cloth or a nonwovenfabric. In this case, the thickness of the polyurethane film itself maybe further thinner than 10 μm.

A polyurethane plate can be produced by using the polyurethane relatedto the first aspect of the present invention. In that case, the upperlimit of that plate thickness is not specifically limited, but the lowerlimit is usually 0.5 mm, preferably 1 mm and more preferably 3 mm.

[Molecular Weight]

The molecular weight of the polyurethane related to the first aspect ofthe present invention is adjusted according to the applications and doesnot require specific limitations; however, it is preferred to be50,000-500,000, especially 100,000-300,000, of number average molecularweight (Mn) from standard polystyrene calculation measured by the GPC.If the molecular weight is smaller than aforementioned lower limit,enough strength and hardness may not be obtained, and if it is largerthan aforementioned upper limit, deterioration of the handlingproperties such as processabilities tends to occur.

[Tensile Elongation at Break]

The tensile elongation at break of the polyurethane related to the firstaspect of the present invention, using a strip sample of 10 mm in width,100 mm in length, and approximately 50 to 100 μm in thickness, with 50mm distance between chucks and tensile speed of 500 mm/min, measured atthe temperature of 23° C., relative humidity 55%, has the lower limitthat is typically 50%, preferably 100%, more preferably 150%, and theupper limit that is typically 400%, preferably 350%, more preferably300%. If the tensile elongation at break is smaller than aforementionedlower limit, deterioration of the handling properties such asprocessabilities tends to occur, and if it is larger than aforementionedupper limit, enough strength and hardness may not be obtained.

[100% Modulus]

The 100% modulus of the polyurethane related to the first aspect of thepresent invention, using a sample strip of 10 mm in width, 100 mm inlength, and approximately 50 to 100 μm in thickness, with 50 mm distancebetween chucks and tensile speed of 500 mm/min, measured at thetemperature of 23° C., relative humidity 55%, has the lower limit thatis typically 10 MPa or more, preferably 15 MPa or more, more preferably20 MPa or more, and the upper limit that is typically 200 MPa or less,preferably 150 MPa or less, more preferably 100 MPa or less. If the 100%modulus is smaller than aforementioned lower limit, enough strength andhardness may not be obtained, and if it is larger than aforementionedupper limit, deterioration of the handling properties such asprocessabilities tends to occur.

[Creep Property]

The creep property (((L−50)/50)×100(%)) of the polyurethane related tothe first aspect of the present invention, using a sample prepared bycreating a polyurethane film with 100 μm in thickness, cut it into a 10mm-wide strip with marked reference line at every 50 mm, and measuredthe length of reference line (L mm) when 1 MPa of load onto the lengthdirection has been applied for 16 hours and is removed, with constanttemperature and humidity of 23° C./relative humidity 55% RH, does nothave specific lower limit, although the lower is better, and istypically 5%, preferably 2%, more preferably 1%, and the upper limit istypically 20%, preferably 10%. If the creep property is smaller thanaforementioned lower limit, the viscosity of polyurethane becomes highand the load of process may be increased, and if it is larger thanaforementioned upper limit, enough strength and hardness may not beobtained.

[Hardness]

The polyurethane related to the first aspect of the present inventionhas characteristics that can obtain higher degree of hardness as it hasa structure of higher rigidity (A). Specifically, for example, when afilm sample with approximately 50-100 μm in thickness is fixed on thetester (II-type, Gakushin-Type), then perform the friction test for 500reciprocations at 4.9 N load according to the JIS L 0849, the upperlimit of the weight reduction ratio represented in {(Sample weightbefore test−Sample weight after test)/(Sample weight before test)}×100)is typically 2%, preferably 1.5%, more preferably 1.0%. Whereas, theupper limit of this weight reduction ratio is usually 0.1%, preferably0.05%, more preferably 0.01%.

In addition, if it is represented in pencil hardness, that is measuredaccording to the JIS K-5600-5-4 as a guideline, this film form sampletypically has the hardness of 6B or more, preferably 4B or more, morepreferably 3B or more.

[Applications]

The polyurethane related to the first aspect of the present inventioncan develop various characteristics and is available in broadapplications such as the foam, elastomer, paint, fiber, adhesive, floormaterial, sealant, medical material, artificial leather, water-typepolyurethane paint, etc.

Especially, when the high rigidity polyurethane related to the firstaspect of the present invention is used in the applications such asartificial leather, synthetic leather, water-type polyurethane,adhesive, medical material, floor material, coatings, etc, because ofits high ability in the friction resistance and blocking resistanceabilities, it is not physically easily scratched, and it contribute thegood surface characteristics that do not be deteriorated due to thefriction.

The polyurethane related to the first aspect of the present inventioncan be used in the cast molding polyurethane elastomer. Specificapplications include the rolls such as rolling mill roll, papermanufacture roll, office equipment, pre-tensioning roll, etc, the solidcasters/tires of fork lift, motor vehicle new tram, trolley, lorry, etc,and the industrial product such as conveyor belt idler, guide roll,pulley, steel pipe lining, rubber screen for ore, gears, connectingrings, liner, impeller of pumps, cyclone cone, and cyclone liner, etc.In addition, a polyurethane related to the first aspect of the presentinvention can also be used in the belt of OA devices, paper feed roll,cleaning blade for copies, snow plow, toothed belt, surf roller, etc.

The polyurethane related to the first aspect of the present inventionalso is applied in the thermoplastic elastomer. For example, it can beused as the tubes and hoses used in the air pressure device for food andmedical fields, painting equipment, analytical instrument, physical andchemical devices, quantitative pump, water treatment device, IndustrialRobot, etc., the spiral tube, and the fire-fighting hoses. In addition,it is used in the various mechanism of transmission, spinning machine,packaging device, printing device, etc. as the belts such as round belt,V-belt, and flat belt. In addition, it also can be used in the heal topor sole of shoe, parts for devices such as coupling, packing,pole-joint, bush, gear, roll, etc, sports goods, leisure goods and beltfor watches. Moreover, it also contains the automobile parts such as theoil stopper, gear box, spacer, chassis parts, interiors, tire-chainreplacement product, etc. In addition, it can be used for the films suchas the keyboard film and the automotive film, curl code, cable sheath,bellow, carrier belt, flexible container, binder, artificial leather,dipping product, adhesion, etc.

The polyurethane related to the first aspect of the present inventioncan be applied in the application of solvent-based two-component paint,and can be applied to the polyurethane related to the first aspect ofthe present invention can also be applied in the application as thewoodworking products, including the musical instruments, family altar,furniture, decorated plywood board, sport gear, etc. And also beavailable in the automobile repairs as the tar-epoxy urethane.

The polyurethane related to the first aspect of the present inventioncan be used as a component such as the moisture-curing-typeone-component paint, blocked isocyanate type solvent paint, alkyd resinpaint, urethane modified synthetic resin paint, UV cure paint,water-based urethane paint, etc., and for example, it can be applied tothe paint for the plastic bumper, strippable paint, coating agent forelectromagnetic tape, floor tile, floor material, paper, overprintvarnish for wooden printing films, varnish for woods, coil coating forhigh processing, optical fiber protection coating, solder resist, topcoating for metal print, base coating for evaporation coating, whitecoating for canned food and so on.

The polyurethane related to the first aspect of the present inventioncan also be applied as adhesive in the use of food packaging, shoes,footwear, magnetic tape binder, decorative paper, wood, structuralmember, etc., and also be used as the component of the low temperatureadhesive and hot-melt.

In the form of using the polyurethane related to the first aspect of thepresent invention as the adhesive, there are not specific limitations,therefore it is possible to use obtained polyurethane as the solventadhesive by resolving into the solvent or as the hot-melt adhesivewithout using the solvent.

For the case that uses the solvent, there are no limitations regardingthe solvents unless it is suitable for the characteristics of theurethane obtained, and both the water-based and organic-based solventcan be used. Especially, due to the reduction of the environmentalloads, there are increasing demands for the water-based adhesives thatare water-based polyurethane emulation is solved or dispersed into thewater-based solvent, and the polyurethane related to the first aspect ofthe present invention is preferably suited used in that objective.Moreover, the adhesives that is produced from the polyurethane relatedto the first aspect of the present invention is able to mix theadditives and auxiliaries used in the normal adhesives according to needwithout restriction. The examples of additives include pigment,anti-blocking agent, dispersion stabilizer, viscosity regulator,labeling agent, antigelling agent, light stabilizer, antioxidizingagent, ultraviolet absorber, heat resistance improver, inorganic ororganic bulking agent, plasticizer, lubricant, antistatic agent,reinforcing material, catalyst, and a known method such as agitating anddispersion and so on as a method for adding these additives can beadopted.

The adhesives related to the first aspect of the present invention thatis obtained by abovementioned method can effectively bond the metalmaterials such as iron, copper, aluminum, ferrite and coated plate,etc., and resin materials such as acrylate resin, polyester resin, ABSresin, polyamide resin, polycarbonate resin, vinyl chloride resin andthe inorganic materials such as glass and ceramics, etc.

The polyurethane related to the first aspect of the present inventioncan be used, as binder, in the magnetic recording medium, inks, castmetals, burned brick, graft material, micro capsule, granulatedfertilizer, granulated agrichemical, polymer cement mortar, resinmortar, rubber chip binder, recycle foam, glass fiber sizing, etc.

The polyurethane related to the first aspect of the present inventioncan be used, as a component of fiber-processing agent, in the processfor giving shrink resistant, wrinkle-free, and water repellent, etc tothe fiber.

When the polyurethane related to the first aspect of the presentinvention is used as the elastic fiber, the method of fibrillization ofelastic fiber can be performed without particular limitations if fibercan be formed. For example, it is possible to employ the melt spinningmethod that is to pelletization once, then let them melt, then directlyspin through the spinneret. If the elastic fiber is obtained from thepolyurethane related to the first aspect of the present invention by themelt spinning, spinning temperature is preferably 250° C. or less, morepreferably between 200° C. or more and 235° C. or less.

The polyurethane elastic fiber related to the first aspect of thepresent invention can be used as the bare yarn without modification orcan be coated with the other fibers and be used as the coated yarn.Other fibers include the previously known fibers such as polyamidefiber, wool, cotton, polyester-fiber, etc, and especially, thepolyester-fiber is preferably used in the present invention. Inaddition, the elastic fiber related to the first aspect of the presentinvention can contain the disperse dye of dyeing type.

The polyurethane related to the first aspect of the present inventioncan be used as the sealant caulking for concrete wall, inducing joint,frame and sash materials, wall type PC joint, ALC joint, boards joint,composite glass sealant, thermal-protection sash sealant, automobilesealant, etc.

The polyurethane related to the first aspect of the present inventioncan be used as the medical materials, including the blood compatiblematerial such as tube, catheter, artificial heart, artificial bloodvessel, artificial valve etc, as well as the disposable materials suchas catheter, tube, bag, surgical gloves, artificial kidney pottingmaterial, etc.

The polyurethane related to the first aspect of the present invention,by terminal modifications, can be used as the raw materials for the UVcurable paint, electron beam curable paint, photosensitive resincomposition for flexographic printing plate, light curing type coveringmaterial composition for optical fiber, etc.

[Active-Energy Radiation Curable Polymer Composition]

An active-energy radiation curable polymer composition can be producedby using the polycarbonate diol related to the first aspect of thepresent invention.

The active-energy radiation curable polymer composition related to thefirst aspect of the present invention contains an urethane(meth)acrylateoligomer which is obtained from a raw material containing thepolycarbonate diol related to the first aspect of the present invention,a polyisocyanate, and a hydroxyalkyl(meth)acrylate. Where, an optimumaspect as polyisocyanate, hydroxyalkyl(meth)acrylate, and theobtained-urethane (meth)acrylate oligomer is the same aspect as theactive-energy radiation curable polymer composition related to thesecond aspect of the present invention to be discussed later.

[Active Energy Ray-Curable Polymer Composition]

Another aspect of the present invention is an active-energy radiationcurable polymer composition. The active-energy radiation curable polymercomposition related to the second aspect of the present inventioncontains an urethane(meth)acrylate oligomer. The urethane(meth)acrylateoligomer which is used by the second aspect of the present invention isa compound having one or more radical polymerizable (meth)acryloylgroups and at least two urethane bonds. The urethane (meth)acrylateoligomer is more excellent than other well-known active-energy radiationcurable oligomer such as an epoxy (meth)acrylate-based oligomer, anacryl(meth)acrylate-based oligomer, etc. in that a cured materialirradiated by the active energy ray has a well-balanced tensile strengthand excellent tensile elongation, and its surface hardening is excellentas a composition, and scarcely leaving tackiness.

The urethane(meth)acrylate oligomer in the second aspect of the presentinvention is obtained from a raw material containing polyisocyanate,polycarbonate diol and hydroxyalkyl(meth)acrylate. Theurethane(meth)acrylate oligomer can be either one type or two or moretypes.

The following describes each component of raw materials of theurethane(meth)acrylate oligomer.

(1) Polyisocyanate

A polyisocyanate constituting an urethane(meth)acrylate oligomer in thesecond aspect of the present invention is a compound having one or bothof the substituent groups containing two or more isocyanate groups andisocyanate groups in one molecule (also referred as “isocyanategroups”). One type or two types or more polyisocyanate(s) is allowed. Inone type of polyisocyanates, isocyanate groups may be either the same ordifferent.

The substituent group containing isocyanate group includes alkyl group,alkenyl group, or alkoxyl group having 1 to 5 carbons, containing one ormore isocyanate group(s), for example. The carbon number for theaforementioned alkyl group, etc. as a substituent group containingisocyanate group is preferred to be 1 to 3.

The number average molecular weight of the polyisocyanate is, in termsof balances between strength and elasticity as a cured material obtainedby curing the active-energy radiation curable polymer composition,preferably 100 or more, more preferably 150 or more, while preferably1,000 or less, and more preferably 500 or less.

The number average molecular weight of the polyisocyanate can beobtained by a calculated value from a chemical formula in case of apolyisocyanate comprising a single monomer, while a calculated valuefrom NCO % in case of a polyisocyanate comprising two types or moremonomers.

The aforementioned polyisocyanate includes an aliphatic polyisocyanate,a polyisocyanate having an alicyclic structure, and an aromaticpolyisocyanate, for example.

The aliphatic polyisocyanate is a compound having an aliphatic structureand two or more isocyanate groups bonded thereto. The aliphaticpolyisocyanate is preferred because it increases weather resistance andgives flexibility to the cured material obtained by curing theactive-energy radiation curable polymer composition. The aliphaticstructure in an aliphatic polyisocyanate is not specifically limited,but a straight- or branched-chain alkylene group having 1 to 6 carbonsis preferred. Such an aliphatic polyisocyanate includes an aliphaticiisocyanate such as tetramethylene diisocyanate, hexamethylenediisocyanate, trimethyl hexamethylene diisocyanate, and dimer aciddiisocyanate, and aliphatic triisocyanate such astris(isocyanatehexyl)isocyanurate, for example.

The polyisocyanate is preferred to include a polyisocyanate having analicyclic structure in terms of mechanical strength and it increasesweather resistance and contamination resistance of a cured materialobtained by curing the active-energy radiation curable polymercomposition related to the second aspect of the present invention.

The polyisocyanate having an alicyclic structure is a compound having analiphatic structure and two or more isocyanate groups bonded thereto.The alicyclic structure in a polyisocyanate having an alicyclicstructure is not specifically limited, but a cycloalkylene group having3 to 6 carbons is preferred. A polyisocyanate having an alicyclicstructure includes diisocyanate having an alicyclic structure such asbis(isocyanatemethyl)cyclohexane, cyclohexanediisocyanate,bis(isocyanatecyclohexyl)metane, and isophorone diisocyanate, andtriisocyanate having an alicyclic structure such astris(isocyanateisophorone)isocyanurate.

A polyisocyanate having an alicyclic structure is preferred in terms ofhigher weather resistance of a cured material obtained by curing anactive-energy radiation curable polymer composition, while apolyisocyanate having such an alicyclic structure includesbis(isocyanatemethyl)cyclohexane, cyclohexanediisocyanate,bis(isocyanatecyclohexyl)metane, and isophorone diisocyanate.

The aromatic polyisocyanate is a compound having an aromatic structureand two or more isocyanate groups bonded thereto. The aromatic structurein an aromatic polyisocyanate is not specifically limited, but divalentaromatic group having 6 to 13 carbons is preferred. Such an aromaticpolyisocyanate includes aromatic series diisocyanate such astolylenediisocyanate, xylylene diisocyanate, diphenylmethanediisocyanate, m-phenylenediisocyanate, and naphthalenediisocyanate, forexample.

The aromatic polyisocyanate is preferred in terms of higher mechanicalstrength of the aforementioned cured material, for example, while sucharomatic polyisocyanate includes tolylenediisocyanate anddiphenylmethane diisocyanate.

(2) Polycarbonate Diol

The polycarbonate diol constituting the urethane(meth)acrylate oligomerin the second aspect of the present invention is the same polycarbonatediol as the first aspect. However, when the polycarbonate diol relatedto the first aspect is applied as polycarbonate diol constituting theurethane(meth)acrylate oligomer related to the second aspect, thepreferred range of the polycarbonate diol may be different from thepreferred range of the polycarbonate diol alone related to the firstaspect, while their differences are mainly discussed below.

The polycarbonate diol constituting the urethane(meth)acrylate oligomerin the second aspect of the present invention is a compound of whichnumber average molecular weight is 500 or more and 5,000 or less, andincludes 10 mass % or more of repeating unit represented by thefollowing formula (A). The aforementioned polycarbonate diol has atleast two hydroxyl groups in that molecular chain, or preferably each onboth terminals of the molecular chain. The polycarbonate diol may be onetype or two or more types.

The structure other than the above Structure (A) is exemplified as astructure represented by the following formula (B) (hereinafter, astructure represented by the formula (B) may be referred to as“Structure (B)”), for example.). The Structure (B) may be continuing inthe aforementioned polycarbonate diol, may consist in regular intervals,or may be unevenly distributed.

In formula (B), X represents a divalent group having 1 to 15 carbonswhich may contain hetero atom. This group may include a straight- orbranched-chained chain group, ring group or any of these structures. Acarbon number as an element constituting X is preferably 10 or less andmore preferably 6 or less in terms of mechanical strength of the curedfilm to be obtained.

Specific examples of an X group include a group to be generated if adiol giving Structure (B) is used in producing the polycarbonate diol.The diol may be one type or two or more types. Such a diol includes adiol named at the first aspect.

X in formula (B) is preferred to be a divalent group having 6 carbons interms of mechanical strength of a cured film to be obtained andindustrial availability. Such an X includes an X derived from1,6-hexanediol or 3-methyl-1,5-pentanediol as the aforementioned diol.

The amount of a structure other than the aforementioned structure (A) inthe aforementioned polycarbonate diol may be in the range which canexhibit an effect by those other structures in addition to the effect ofthe present invention, so it can be decided arbitrarily according tothose other structures.

The number average molecular weight of the aforementioned polycarbonatediol is 500 or more and 5,000 or less because the urethane(meth)acrylateoligomer has an appropriate viscosity and exhibits preferableworkability, and in terms of mechanical strength and highercontamination resistance of the cured material obtained by curing theactive-energy radiation curable polymer composition. The number averagemolecular weight of the aforementioned polycarbonate diol is preferably3,000 or less, more preferably 2,000 or less and further preferably1,500 or less. The number average molecular weight of the aforementionedpolycarbonate diol is preferably 800 or more, and more preferably 1,000or more in terms of the aforementioned points. When the number averagemolecular weight of the aforementioned polycarbonate diol is smaller,the aforementioned workability is enhanced, and mechanical strength andcontamination resistance of the aforementioned cured material may beimproved. When the number average molecular weight of the aforementionedpolycarbonate diol is larger, a flexibility, which can followtransformation during 3D process of the aforementioned cured material,tends to be improved.

A hydroxyl value (OH value) of the aforementioned polycarbonate diol ispreferred to be 20 mgKOH/g or more and 250 mgKOH/g or less in terms ofmechanical strength and higher contamination resistance of a curedmaterial obtained by curing the active-energy radiation curable polymercomposition. The hydroxyl value (OH value) of the aforementionedpolycarbonate diol is preferred to be 150 mgKOH/g or less in terms ofthe aforementioned points. The hydroxyl value of the aforementionedpolycarbonate diol is preferably 35 mg/KOH/g or more, more preferably 55mg/KOH/g or more and further preferably 75 mg/KOH/g or more in terms ofthe aforementioned points. When the hydroxyl value of the aforementionedpolycarbonate diol is smaller, a flexibility, which can followtransformation during 3D process of the aforementioned cured material,tends to be improved. When the hydroxyl value of the aforementionedpolycarbonate diol is larger, mechanical strength and contaminationresistance of the aforementioned cured material tends to be improved.The hydroxyl value (OH value) of the aforementioned polycarbonate diolcan be measured by the following method.

The average number of hydroxyl groups per molecule of the aforementionedpolycarbonate diol is 2.2 or less in terms of gelation control inproducing an urethane(meth)acrylate oligomer. The average number ofhydroxyl groups per molecule of the aforementioned polycarbonate diol ispreferred to be 2.1 or less in terms of the aforementioned points. Whenthe average number of hydroxyl groups per molecule in the aforementionedpolycarbonate diol exceeds the aforementioned upper limit, gelationoccurs in producing urethane(meth)acrylate oligomer. Consequently, notonly the urethane(meth)acrylate oligomer but also a reactor may bedamaged and the obtained active-energy radiation curable polymercomposition includes a gel and has higher viscosity and causes worsecoating properties, which is not preferred. The average number ofhydroxyl groups per molecule in the aforementioned polycarbonate diol isnot limited, but is preferably 1.0 or more, more preferably 1.5 or moreand further preferably 1.8 or more in order to maintain the molecularweight of the aforementioned urethane(meth)acrylate oligomer within atarget range, and to make a well-balanced cured film obtained from anactive-energy radiation curable polymer composition containing theaforementioned oligomer regarding a 3D processing characteristic andcontamination resistance. When the average number of hydroxyl values permolecule in the aforementioned polycarbonate diol is lower than theaforementioned lower limit, the molecular weight tends not to be higherduring a reaction with diisocyanate, while an urethane(meth)acrylateoligomer cannot have a target molecular weight, a well-balanced curedfilm cannot be obtained from the active-energy radiation curable polymercomposition containing the aforementioned oligomer regarding a 3Dprocessing characteristic and contamination resistance.

That is, the average number of hydroxyl groups per molecule in theaforementioned polycarbonate diol is preferably within 2.*0.2, morepreferably 2.0*0.1, and further preferably 2.0.

The average number of hydroxyl groups per molecule in the aforementionedpolycarbonate diol can be calculated by the average number of molecularweight and a hydroxyl value which are obtained by the following method.

The aforementioned polycarbonate diol containing the aforementionedstructure (A) can be produced by an esterification reaction of a diolcomponent containing isosorbide, and its stereoisomers such asisomannide and isoidide and diester carbonate

(3) Hydroxyalkyl(meth)acrylate

The hydroxyalkyl(meth)acrylate constituting the urethane(meth)acrylateoligomer in the second aspect of the present invention is a compoundhaving one or more hydroxyl group(s), one or more (meth)acryloylgroup(s) and a hydrocarbon group having 1 to 30 carbons. Thehydroxyalkyl(meth)acrylate may be one type or two or more types.

The aforementioned hydroxyalkyl(meth)acrylate may include2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,4-hydroxybutyl(meth)acrylate, 6-hydroxyhexyl(meth)acrylate,cyclohexanedimethanolmono(meth)acrylate, or a product of additionreaction of 2-hydroxyethyl(meth)acrylate with a caprolactone, a productof addition reaction of 4-hydroxybutyl(meth)acrylate with caprolactone,a product of addition reaction of glycidyl ether with (meth)acryl acid,mono(meth)acrylate form of glycol, pentaerythritoltri(meth)acrylate, anddipentaerythritolpenta(meth)acrylate.

Among the above, hydroxyalkyl(meth)acrylate having an alkylene grouphaving 2-4 carbons between (meth)acryloyl group and hydroxyl group suchas 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,4-hydroxybutyl(meth)acrylate is preferred in terms of mechanicalstrength of the obtained cured film.

The molecular weight of the aforementioned hydroxyalkyl(meth)acrylate ispreferred to be 40 or more, and more preferred to be 80 or more, whilein terms of mechanical strength of the obtained cured film, 800 or lessis preferred and 400 or less is further preferred. If the aforementionedhydroxyalkyl(meth)acrylate is a product of the aforementioned additionreaction or a polymer, the aforementioned molecular weight means anumber average molecular weight.

(4) Others

The urethane(meth)acrylate oligomer in the second aspect of the presentinvention may contain other components in its raw material as long aseffects of the present invention can be obtained. Those other componentsinclude a high molecular weight polyol of which number average molecularweight is over 500 excluding the polycarbonate diol containing theaforementioned structure (A), and a low molecular weight polyol of whichnumber average molecular weight is 500 or less, and a chain extender.

The aforementioned high molecular weight polyol is a compound of whichnumber average molecular weight is over 500 and contains two or morehydroxyl groups (excluding the polycarbonate diol containing theaforementioned structure (A)). The aforementioned high molecular weightpolyol may be one type or two or more types. Those high molecular weightpolyols include polyether diol, polyesterdiol, polyether ester diol, andthe polycarbonate diol other than the polycarbonate diol including theaforementioned structure (A), polyolefin polyol and silicone polyol.

The aforementioned polyether diol includes a compound which can beobtained by ring-opening polymerization of cyclic ether, such aspolyethylene glycol, polypropylene glycol, and polytetramethyleneglycol.

The aforementioned polyester diol includes a compound which can beobtained by polycondensation of dicarboxylic acid or its anhydride andlow-molecular weight diol, such as polyethylene adipate, polypropyleneadipate, polybutylene adipate, polyhexamethylene adipate, andpolybutylene sebacate. The aforementioned ester diol includes a compoundwhich can be obtained by polycondensation of lactone with low-molecularweight diol such as polycaprolactone and polymethyl valerolactone. Theaforementioned dicarboxylic acid includes succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, andphthalic acid, while anhydride of the dicarboxylic acid includes thoseanhydrides, for example, the aforementioned low-molecular weight diolincludes ethylene glycol, diethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol,1,4-butanediol, polytetramethyleneglycol, 1,5-pentanediol,1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol,2-ethyl-1,3-hexane glycol, 2,2,4-trimethyl-1,3-pentanediol,3,3-dimethylol heptane, 1,9-nonanediol, 2-methyl-1,8-octanediol,cyclohexanedimethanol, and bishydroxyethoxy benzene.

The aforementioned polyether ester diol includes a compound obtained byring-opening polymerization of a cyclic ether with the aforementionedpolyester diol, and a compound obtained by polycondensation of theaforementioned polyether diol and the aforementioned dicarboxylic acidsuch as poly(polytetramethylene ether) adipate.

The aforementioned other polycarbonate diol includes polybutylenecarbonate, a polyhexamethylene carbonate,poly(3-methyl-1,5-pentylene)carbonate, etc. and those copolymers whichare obtained by removing glycol or alcohol from the aforementionedlow-molecular weight diol and alkylene carbonate or dialkyl carbonate.

The aforementioned polyolefin polyol is polyolefin having two or morehydroxyl groups. The aforementioned polyolefin polyol may be one type ortwo or more types. The aforementioned polyolefin polyol includes polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprenepolyol, for example.

The aforementioned silicone polyol is silicone having two or morehydroxyl groups. The aforementioned silicone polyol may be one type ortwo or more types. The aforementioned silicone polyol includespolydimethylsiloxane polyol.

Among them, the aforementioned high-molecular weight polyol is preferredto be the aforementioned other polycarbonate diol in terms of higherweather resistance and mechanical strength of the cured materialobtained by curing the active-energy radiation curable polymercomposition.

When the number average molecular weight of the other aforementionedpolycarbonate diol is small, viscosity of the urethane(meth)acrylateoligomer is not significantly increased and its workability isfavorable, while higher weather resistance and higher mechanicalstrength of the cured material obtained by curing the active-energyradiation curable polymer composition can be expected. Because of thesepoints, the number average molecular weight of the aforementioned otherpolycarbonate diol is preferably 10,000 or less, more preferably 5,000or less and further preferably 2,000 or less.

The aforementioned low molecular weight polyol is a compound of whichnumber average molecular weight is 500 or less and contains two or morehydroxyl groups (excluding the polycarbonate diol containing theaforementioned structure (A)). The aforementioned low molecular weightpolyol may be one type or two or more types. These low molecular weightpolyols include aliphatic diol such as ethylene glycol, diethyleneglycol, triethylene glycol, propylene glycol, dipropylene glycol,1,2-propane diol, 1,3-propane diol, 2-methyl-1,3-propane diol, neopentylglycol, 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentane diol,2,2,4-trimethyl-1,5-pentane diol, 2,3,5-trimethyl-1,5-pentan ediol,1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol,3,3-dimethylol heptane, 1,8-octanediol, 2-methyl-1,8-octane diol, and1,9-nonanediol; alicyclic diol such as cyclopropane diol, cyclopropanedimethanol, cyclopropane diethanol, cyclopropane dipropanol,cyclopropane dibutanol, cyclopentane diol, cyclopentane dimethanol,cyclopentane diethanol, cyclopentane dipropanol, cyclopentane dibutanol,cyclohexanediol, cyclohexane dimethanol, cyclohexane diethanol,cyclohexane dipropanol, cyclohexane dibutanol, cyclohexene diol,cyclohexene dimethanol, cyclohexene diethanol, cyclohexene dipropanol,cyclohexene dibutanol, cyclohexadiene diol, cyclohexadiene dimethanol,cyclohexadiene diethanol, cyclohexadiene dipropanol, cyclohexadienedibutanol, hydrogenated bisphenol A, tricyclodecane diol, and adamantyldiol; aromatic series-based diol such as bishydroxyethoxy benzene,bishydroxyethyl terephthalate, and bisphenol-A; dialkanol amine such asN-methyldiethanolamine; pentaerythritol; sorbitol; mannitol; glycerin;and trimethylolpropane.

Among them, the aforementioned low-molecular weight polyol is preferredto be aliphatic diol or alicyclic diol in terms of the weatherresistance of the cured film to be obtained. In particular, forapplications where mechanical strength of the cured film is required,the aforementioned low-molecular weight polyol is especially preferredto be polyol having 1-4 carbons between hydroxyl groups such as ethyleneglycol, propylene glycol, 1,2-propanediol, 1,3-propanediol,2-methyl-1,3-propanediol, neopentyl glycol, 1,2-butanediol,1,3-butanediol, and 1,4-butanediol; and alicyclic polyol where twohydroxyl groups symmetrically exist against alicyclic structure such as1,4-cyclohexanedimethanol, and hydrogenated bisphenol-A.

The number average molecular weight of the aforementioned low-molecularweight polyol is, in terms of balances between elongation and elasticityas the cured material obtained by curing the active-energy radiationcurable polymer composition, preferably 50 or more, while preferably 250or less, and more preferably 150 or less.

The aforementioned chain extender is a compound having two or moreactive hydrogens which react with isocyanate group. The chain extendermay be one type or two or more types. Such a chain extender includes alow-molecular weight diamine compound of which number average molecularweight is 500 or less for example, aromatic series diamine such as 2,4-or 2,6-tolylene diamine, xylylene diamine, and 4,4′-diphenylmethanediamine; aliphatic diamine such as ethylene diamine, 1,2-propylenediamine, 1,6-hexane diamine, 2,2-dimethyl-1,3-propane diamine,2-methyl-1,5-pentane diamine, 2,2,4- or 2,4,4-trimethyl hexane diamine,2-butyl-2-ethyl-1,5-pentane diamine, 1,8-octane diamine, 1,9-nonanediamine, and 1,10-decane diamine; and alicyclic diamine such as1-amino-3-aminomethyl-3,5,5-trimethyl cyclohexane (IPDA),4,4′-dicyclohexylmethane diamine (hydrogenated MDA),isopropylidenecyclohexyl-4,4′-diamine, 1,4-diaminocyclohexane,1,3-bisaminomethylcyclohexane, and tricyclodecanediamine.

The molecular weight or the number average molecular weight of theaforementioned raw material compound such as the polycarbonate diolcontaining the aforementioned structure (A) can be calculated by the gelpermeation chromatography (hereinafter, referred as “GPC”), while themolecular weight of a compound other than a polyol having the molecularweight distribution can be calculated by a chemical formula or thenumber average molecular weight can be obtained by GPC. The numberaverage molecular weight of a polyol having the molecular weightdistribution at GPC can also be calculated by OH value.

[Calculation of the Number Average Molecular Weight by GPC]

By using GPC (“HLC-8120 GPC” made by TOSOH Corporation), atetrahydrofuran is used as a solvent, a polystyrene as a standardsample, and TSK gel superH1000+H2000+H3000 as a column to measure itsnumber average molecular weight at solution sending speed at 0.5cm³/min. and the column oven temperature at 40° C.

[Calculation of the Number Average Molecular Weight of Polyisocyanate byNCO %]

1 g of polyisocyanate and 20 mL of 0.5 mol/litter dibutylamine toluenesolution is stored in an Erlenmeyer flask, diluted by 100 mL of acetoneto react at 25° C. for 30 min. Then, it is titrated by 0.5 mol/litterhydrochloric acid solution. The titration same as abovementioned isperformed to obtain a blank value, unless the polyisocyanate was notinjected into an Erlenmeyer flask. Then NCO % and the number averagemolecular weight are calculated by the following formula.

NCO %={B1−A1)×0.5×42.02}/(1×1000)×100

A1: The amount of hydrochloric acid solution required for titrating asolution containing polyisocyanate (mL)B1: The amount of hydrochloric acid solution required for titrating ablank solution which does not contain polyisocyanate (mL)

The number average molecular weight of polyisocyanate=(42.02/NCO %)×thenumber of NCO groups contained in one molecule polyisocyanate

[Calculation by OH Value of the Number Average Molecular Weight ofPolyol]

Two gram (2 g) of polyol and 0.5 mol/litter pyridine solution ofphthalic anhydride are stored in an Erlenmeyer flask to react at 100° C.for 2 hours, then diluted by 150 mL of acetone. Then, it is titrated by0.5 mol/litter aqueous sodium hydroxide. The titration same asabovementioned is performed to obtain a blank value, unless the polyolwas not injected into an Erlenmeyer flask. Then OH value and the numberaverage molecular weight are calculated by the following formula.

OH value={(B2−A2)×0.5×56.11×1000}/(2×1000)

A2: The amount of aqueous sodium hydroxide required for titrating asolution containing a polyol (mL)B2: The amount of aqueous sodium hydroxide required for titrating ablank solution which does not contain a polyol (mL)The number average molecular weight of polyol={(56.11×1000)/OHvalue}×the number of functional groups

In the aforementioned formula, “the number of functional groups”indicates the number of OH groups which are contained in one moleculepolyol.

The amount of all isocyanate groups and the amount of all functionalgroups to react with the isocyanate group such as hydroxyl group andamino group in the urethane(meth)acrylate oligomer related to the secondaspect of the present invention are usually equivalent mol theoreticallyand represented by mol %.

Therefore, the amount of the aforementioned polyisocyanate,polycarbonate diol, hydroxyalkyl(meth)acrylate, and other raw materialcompounds in the aforementioned urethane(meth)acrylate oligomer is theamount in which the amount of all isocyanate groups and the amount ofall functional groups to react them in the urethane(meth)acrylateoligomer are the equivalent mol, or 50 to 200 mol % by the functionalgroups relative to the isocyanate groups.

In producing the urethane(meth)acrylate oligomer, the amount ofhydroxyalkyl(meth)acrylate is usually 10 mol % or more, preferably 15mol % or more, more preferably 25 mol % or more, or usually 70 mol % orless, and preferably 50 mol % or less relative to the total amount ofcompounds containing a functional group to react with isocyanate such ashydroxyalkyl(meth)acrylate, the aforementioned polycarbonate diol, theaforementioned high-molecular weight polyol, the aforementionedlow-molecular weight polyol, and a chain extender. According to thisproportion, the molecular weight of the obtained urethane(meth)acrylateoligomer can be controlled. With higher hydroxyalkyl(meth)acrylateproportion, the molecular weight of urethane(meth)acrylate oligomertends to be small, while with lower proportion the molecular weighttends to be large.

Relative to the total amount of the aforementioned polycarbonate dioland the aforementioned high-molecular weight polyol, the amount of theaforementioned polycarbonate diol is preferably 25 mol % or more, morepreferably 50 mol % or more and further preferably 70 mol % or more.When the amount of the aforementioned polycarbonate diol is larger thanthe aforementioned lower limit, hardness and contamination resistance ofthe cured material tends to be excellent, which is preferred.

In addition, relative to the total amount of the aforementionedpolycarbonate diol, the aforementioned high-molecular weight polyol, andthe aforementioned low-molecular weight polyol, the amount of theaforementioned polycarbonate diol is preferably 25 mol % or more, morepreferably 50 mol % or more and further preferably 70 ol % or more. Whenthe amount of the aforementioned polycarbonate diol is larger than theaforementioned lower limit, elongation and weather resistance of thecured material tends to be improved, which is preferred.

If an urethane(meth)acrylate oligomer is a compound containing a chainextender, the amount of all polyols relative to the total amount ofcompounds of the aforementioned polycarbonate diol, the aforementionedhigh-molecular weight polyol, the aforementioned low-molecular weightpolyol, and the chain extender is preferably 70 mol % or more, morepreferably 80 mol % or more, further preferably 90 mol % or more, andespecially preferably 95 mol % or more. When the aforementioned amountof all polyols is larger than the lower limit, its solution stabilitytends to be improved, which is favorable.

In the active-energy radiation curable polymer composition related tothe second aspect of the present invention, the calculated crosslinkingpoints molecular weight of the composition is preferred to be 500 to10,000.

In the present specification, the calculated crosslinking pointsmolecular weight of a composition represents an average value of themolecular weight among an active energy ray reactive group forming anetwork structure among all compositions (hereinafter, may be referredas “crosslinking point”). This molecular weight between calculatednetwork crosslinking point correlates with network planar dimension informing a network structure, while with larger calculated crosslinkingpoints molecular weight, its crosslinking density becomes small. In anactive energy ray curing reaction, when a compound having only oneactive energy ray reactive group (hereinafter, may be referred as“monofunctional compound”) is reacted, a linear polymer molecule isgenerated, while a compound having two or more active energy rayreactive group (hereinafter, may be referred as “multifunctionalcompound”) is reacted, a network structure is formed.

Therefore, an active energy ray reactive group owned by amultifunctional compound is a crosslinking point, the calculatedcrosslinking points molecular weight is calculated mainly by amultifunctional compound having the crosslinking points. Then, amonofunctional compound is treated as exhibiting an effect for extendingthe molecular weight among crosslinking points obtained by themultifunctional compound to calculate the calculated crosslinking pointsmolecular weight. In addition, the calculated crosslinking pointsmolecular weight is calculated, assuming that all active energy rayreactive group has the same reactivity, and all active energy rayreactive groups react when the active energy ray is irradiated.

In a multifunctional compound of single system composition in which onlyone type of multifunctional compound reacts, two times of the averagemolecular weight per one active energy ray reactive group owned by amultifunctional compound is the calculated crosslinking points molecularweight. For example, a bifunctional compound of the molecular weight1,000 is (1000/2)×2=1000, while a trifunctional compound of themolecular weight 300 is (300/3)×2=200.

In a multifunctional compound combined composition in which multipletypes of multifunctional compounds react, average value of respectivecalculated crosslinking points molecular weight of the above singlesystem against the number of all active energy ray reactive groupscontained in the composition is to be the calculated crosslinking pointsmolecular weight of the composition. For example, in a compositioncomprising a mixture of 4 mols of a bifunctional compound of themolecular weight 1,000 and 4 mols of a trifunctional compound of themolecular weight 300, the number of all active energy ray reactivegroups in the composition is 2×4+3×4=20, and the calculated crosslinkingpoints molecular weight is {(1000/2)×8+(300/3)×12}×2/20=520.

When a monofunctional compound is included in a composition,computationally assuming that reaction is made in a position of thecenter of the molecular chain formed by linking each equivalent mol toactive energy ray reactive group of a multifunctional compound (that isa crosslinking point) and linking monofunctional compound to thecrosslinking point, the extended length of the molecular chain by amonofunctional compound at one crosslinking point is half of the valueobtained by dividing the total molecular weight of monofunctionalcompounds by the number of all active energy ray reactive groups inmultifunctional compounds in the composition. Here, the molecular weightbetween calculated network cross-linking points is considered to betwice the average molecular weight per one crosslinking point, so thelength extended by a monofunctional compound against the calculatedcrosslinking points molecular weight calculated for a multifunctionalcompound is the value obtained by dividing the total molecular weight ofthe monofunctional compounds by the number of all active energy rayreactive group of the multifunctional compound in the composition.

For example, in a composition comprising a mixture of 40 mols of amonofunctional compound of the molecular weight 100 and 4 mols of abifunctional compound of the molecular weight 1,000, the number ofactive energy ray reactive groups of the multifunctional compound is2×4=8, and the extended length by the monofunctional compound in thecalculated crosslinking points molecular weight is 100×4/8=500. That is,the calculated crosslinking points molecular weight of the compositionis 1000+500=1500.

Because of these, in a mixture in which a monofunctional compound M_(A)mol of the molecular weight W_(A), f_(B)-functional compound M_(B) molof the molecular weight W_(B), and f_(C)-functional compound M_(C) molof the molecular weight W_(C), the calculated crosslinking pointsmolecular weight of the composition can be represented by the followingformula:

$\begin{matrix}{\frac{\begin{matrix}{{( {\frac{W_{A}M_{A}}{{f_{B}M_{B}} + {f_{C}M_{C}}} + \frac{2W_{B}}{f_{B}}} ) \times f_{B}M_{B}} +} \\{( {\frac{W_{A}M_{A}}{{f_{B}M_{B}} + {f_{C}M_{C}}} + \frac{2W_{C}}{f_{C}}} ) \times f_{C}M_{C}}\end{matrix}}{{f_{B}M_{B}} + {f_{C}M_{C}}} = \frac{{W_{A}M_{A}} + {2W_{B}M_{B}} + {2W_{C}M_{C}}}{{f_{B}M_{B}} + {f_{C}M_{C}}}} & \lbrack {{Mathematical}\mspace{14mu} {formula}\mspace{14mu} 3} \rbrack\end{matrix}$

The calculated crosslinking points molecular weight of the active-energyradiation curable polymer composition related to the second aspect ofthe present invention is preferably 500 or more, more preferably 800 ormore, and further preferably 1,000 or more, while preferably 10,000 orless, more preferably 8,000 or less, further preferably 6,000 or less,much further preferably 4,000 or less, and specially preferably 3,000 orless.

When the calculated crosslinking points molecular weight is 10,000 orless, contamination resistance of the cured film obtained by thecomposition is excellent, and tends to be well-balanced between 3Dprocessing suitability and contamination resistance, which is favorable.When the calculated crosslinking points molecular weight is 500 or more,3D processing suitability of the obtained cured film is excellent, andtends to be well-balanced between 3D processing suitability andcontamination resistance, which is favorable. This is speculated becausethe 3D processing suitability and contamination resistance tend todepend on the distance between crosslinking points in the networkstructure, while with the longer distance, the structure is flexible andeasy to be extended, which is good at 3D processing suitability, andwith the shorter distance the network structure is rigid and good atcontamination resistance.

The urethane(meth)acrylate oligomer related to the second aspect of thepresent invention can be produced by addition reacting theaforementioned polycarbonate diol containing Structure (A) and theaforementioned hydroxyalkyl(meth)acrylate to the aforementionedpolyisocyanate. Here, when the aforementioned high-molecular weightpolyol, the aforementioned low-molecular weight polyol, and theaforementioned chain extender, etc. are used together as its rawmaterial, the urethane(meth)acrylate oligomer related to the secondaspect of the present invention can be produced by addition reacting theother aforementioned raw material compounds to the aforementionedpolyisocyanate. This addition reaction can be conducted by any knownmethod. These methods include the following (1) to (3) approaches.

(1) A prepolymer method, in which isocyanate terminal urethaneprepolymer is obtained by reacting components other than theaforementioned hydroxyalkyl(meth)acrylate under a excess isocyanategroup condition, then the isocyanate terminal urethane prepolymer isreacted by the aforementioned hydroxyalkyl(meth)acrylate.(2) One-shot method, in which all components are added together andreacted together.(3) A method, in which the aforementioned polyisocyanate and theaforementioned hydroxyalkyl(meth)acrylate are reacted at first tosynthesize a urethane (meth)acrylate a prepolymer having a(meth)acryloyl group and isocyanate group in a molecule together, andthen the other raw material components are reacted with the obtainedprepolymer.

Among them, the method (1) is preferred because the aforementionedurethane prepolymer is obtained by urethanizing the aforementionedpolyisocyanate and the aforementioned polycarbonate diol, and theaforementioned urethane(meth)acrylate oligomer has a structure which isobtained by urethanizing a urethane prepolymer having isocyanate groupsat terminals and the aforementioned hydroxyalkyl(meth)acrylate, so themolecular weight can be controlled and acryloyl groups can be introducedto both terminals.

In producing the urethane(meth)acrylate oligomer, a solvent may be usedto adjust viscosity. One type or two or more types of solvents can beused and any known solvent can be used as far as effects of the presentinvention can be obtained. Preferable solvents include toluene, xylene,ethyl acetate, butyl acetate, cyclohexane, methylethylketone, andmethylisobutylketone. Less than 300 parts by mass of the solvent can beusually used relative to 100 parts by mass of the active-energyradiation curable polymer composition.

In producing the urethane(meth)acrylate oligomer, the total amount ofthe aforementioned urethane (meth)acrylate oligomer and its raw materialis preferred to be 20 mass % or more relative to the total amount, andmore preferred to be 40 mass % or more. The upper limit of this totalamount is 100 mass %. When the total amount of theurethane(meth)acrylate oligomer and its raw material is 20 mass % ormore, its reaction speed gets higher and its producing efficiency tendsto be improved, which is preferred.

In producing the urethane(meth)acrylate oligomer, the reactiontemperature is usually 20° C. or more, preferably 40° C. or more, andmore preferably 60° C. or more. When the reaction temperature is 20° C.or more, its reaction speed gets higher and its producing efficiencytends to be improved, which is preferred. Further it is usually 120° C.or less and preferably 100° C. or less. When the reaction temperature is120° C. or less, a side reaction such as allophanate reaction can besuppressed, which is preferred. When a solvent is included in a reactionsolution, a temperature below the boiling point of that solvent ispreferred, and when (meth)acrylate is contained, 70° C. or less ispreferred in terms of prevention of reaction of (meth)acryloyl group.The reaction time is usually about 5 to 20 hours.

A catalyst for addition reaction in producing an urethane(meth)acrylateoligomer can be selected from the range which an effect of the presentinvention can be obtained, and includes dibutyltin laurate, dibutyltindioctoate, dioctyltin dilaurate, and dioctyltin dioctoate. The additionreaction catalyst may be one type or two or more types. The additionreaction catalyst is preferred to be the dioctyltin dilaurate among themin terms of environmental adaptability, catalyst activity andpreservation stability.

In producing the urethane(meth)acrylate oligomer, if (meth)acryloylgroup is included in its reactive solution, a polymerization inhibitorcan be used together. Such a polymerization inhibitor can be selectedfrom the range in which an effect of the present invention can beobtained, and includes phenols such as hydroquinone, hydroquinonemonoethyl ether, and dibutylhydroxy toluene, amines such asphenothiazine, and diphenylamine, dibutyl dithiocarbamate, copper saltsuch as copper, manganese salt such as manganic acetate, nitro compound,and nitroso compound. The polymerization inhibitor may be one type ortwo or more types. Phenols is preferred among them as the polymerizationinhibitor.

Preparation ratio of each raw material component is substantially equalto the urethane(meth)acrylate oligomer composition related to the secondaspect of the above present invention. Preparation ratio of each rawmaterial component is the same as the urethane(meth)acrylate oligomercomposition related to the second aspect of the above present invention,for example.

The active-energy radiation curable polymer composition related to thesecond aspect of the present invention may contain other componentsother than the aforementioned urethane (meth)acrylate oligomer as longas an effect of the present invention can be obtained. Those othercomponents include an active energy ray reactive monomer, an activeenergy ray curable oligomer, a polymerization initiator, aphotosensitization agent, addition agent, and a solvent.

In the active-energy radiation curable polymer composition related tothe second aspect of the present invention, the amount of theaforementioned urethane(meth)acrylate oligomer is preferably 40 mass %or more and more preferably 60 mass % or more, relative to the totalamount of active energy ray reactive components containing theaforementioned urethane(meth)acrylate oligomer. The upper limit of thisamount is 100 mass %. When the contained urethane(meth)acrylate oligomeramount is 40 mass % or more, an excellent hardness can be obtained, itsmechanical strength as a cured material is not too high, and its 3Dprocessing suitability tends to improve, which is preferable.

In the active-energy radiation curable polymer composition related tothe second aspect of the present invention, the larger amount of theaforementioned urethane(meth)acrylate oligomer is preferred in terms ofelongation and film making property, while the smaller amount ispreferred in terms of lower viscosity. From these points of view, theamount of the aforementioned urethane(meth)acrylate oligomer ispreferably 50 mass % or more, and more preferably 70 mass % or more,relative to the total amount of all components containing othercomponents in addition to the aforementioned active energy ray reactivecomponents. The upper limit of the aforementioned urethane(meth)acrylateoligomer is 100 mass %, and the aforementioned amount is preferred to belower than that amount.

In the active-energy radiation curable polymer composition related tothe second aspect of the present invention, the total amount of theaforementioned active energy ray reactive components containing theaforementioned urethane(meth)acrylate oligomer is preferably 60 mass %or more, more preferably 80 mass % or more, further preferably 90 mass %or more, and much further preferably 95 mass % or more relative to thetotal amount of the composition in terms of excellent curing speed andsurface curing as a composition and tackiness scarcely left. The upperlimit of the aforementioned amount is 100 mass %.

As the aforementioned energy ray reactive monomer, any known activeenergy reactive monomer can also be used as long as an effect of thepresent invention can be obtained. Such an active energy reactivemonomer can be used in order to adjust hydrophobic properties of theurethane(meth)acrylate oligomer and physical properties such as hardnessand elongation of a cured material when the obtained composition is madeto be the cured material. The active energy ray reactive monomer can beone type or two or more types.

These active energy ray reactive monomers include vinyl ethers,(meth)acrylamides, and(meth)acrylates for example, and specificallyaromatic vinyl monomers such as styrene, α-methylstyrene,α-chrolostyrene, vinyl toluene, and divinyl benzene; vinyl estermonomers such as vinyl acetate, vinyl butyrate, N-vinyl formamide,N-vinyl acetamide, N-vinyl-2-pyrolidone, N-vinyl caprolactam, and adipicacid divinyl; vinyl ethers such as ethyl vinyl ether, phenyl vinylether; allyl compounds such as diallyl phthalate, trimethylolpropanediallyl ether, allyl glycidyl ether; (meth)acrylamides such asacrylamide, N, N-dimethyl acrylamide, N, N-dimethyl methacrylamide,N-methylolacrylamide, N-methoxymethylacrylamide,N-butoxymethylacrylamide, N-t-butylacrylamide, acryloylmorpholine,methylenebisacrylamide; monofunctional (meth)acrylate such as(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl(meth)acrylate, n-butyl-(meth)acrylate, i-butyl-(meth)acrylate,t-butyl-(meth)acrylate, hexyl (meth)acrylate,2-ethylhexyl-(meth)acrylate, lauryl (meth)acrylate, stearyl(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, morpholyl(meth)acrylate, 2-hydroxyethyl-(meth)acrylate,2-hydroxypropyl-(meth)acrylate, 4-hydroxybutyl-(meth)acrylate, glycidyl(meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl(meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate,phenoxyethyl (meth)acrylate, tricyclodecane (meth)acrylate,dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate,dicyclopentanyl (meth)acrylate, allyl (meth)acrylate, 2-ethoxyethyl(meth)acrylate, isobornyl (meth)acrylate, (meth)acrylate phenyl; andmultifunctional (meth)acrylate such as ethylene glycol di(meth)acrylate,diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate,tetraethylene glycol di(meth)acrylate, polyethylene glycoldi(meth)acrylate (n=5 to 14), propylene glycol di(meth)acrylate,dipropylene glycol di(meth)acrylate, tripropylene glycoldi(meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropyleneglycol di(meth)acrylate (n=5 to 14), 1,3-butyleneglycol-di(meth)acrylate, 1,4-butanediol-di(meth)acrylate, polybutyleneglycol di(meth)acrylate (n=3 to 16), poly(1-methyl butylene glycol)di(meth)acrylate (n=5 to 20), 1,6-hexanediol di(meth)acrylate,1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate,hydroxypivalic acid neopentyl glycol di(meth)acrylate ester,dicyclopentane diol di(meth)acrylate, tricyclodecane di(meth)acrylate,trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate,dipentaerythritol penta(meth)acrylate, dipentaerythritolhexa(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate,trimethylolpropane trioxypropyl(meth)acrylate, trimethylolpropanepolyoxyethyl (meth)acrylate, trimethylolpropanepolyoxypropyl(meth)acrylate, tris(2-hydroxyethyl) isocyanuratetri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate di(meth)acrylate,ethylene oxide adduct bisphenol A di(meth)acrylate, ethylene oxideadduct bisphenol F di(meth)acrylate, propylene oxide adduct bisphenol Adi(meth)acrylate, propylene oxide adduct bisphenol F di(meth)acrylate,tricyclodecane dimethanol di(meth)acrylate, bisphenol A epoxydi(meth)acrylate, and bisphenol F epoxy di(meth)acrylate.

Among them, for an application in which coating properties are requiredin a composition related to the second aspect of the present invention,monofunctional (meth)acrylate having ring structure in its molecule ispreferred such as (meth)acryloylmorpholine, tetrahydrofurfuryl(meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate,trimethylcyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate,tricyclodecane (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl(meth)acrylate, and mono(meth)acrylamide, while for an application inwhich mechanical strength is required for the obtained cured material,multifunctional (meth)acrylate such as 1,4-butanediol-di(meth)acrylate,1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate,neopentyl glycol di(meth)acrylate, tricyclodecane di(meth)acrylate,trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate,pentaerythritol tetra(meth)acrylate, dipentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, anddipentaerythritol hexa(meth)acrylate are preferred.

In an active-energy radiation curable polymer composition related to thesecond aspect of the present invention, the amount of the aforementionedactive energy ray reactive monomer is preferred to be 50 mass % or less,more preferably 30 mass % or less, further preferably 20 mass % or less,and specially further preferably 10 mass % or less relative to the totalamount of the composition in terms of physical properties adjustmentsuch as viscosity adjustment of the composition, hardness and elongationof the cured material.

The aforementioned active energy ray curable oligomer can be one type ortwo or more types. The aforementioned active energy ray curable oligomerincludes epoxy (meth) acrylate oligomer and acrylic (meth) acrylateoligomer.

In an active-energy radiation curable polymer composition related to thesecond aspect of the present invention, the amount of the aforementionedactive energy ray reactive oligomer is preferred to be 50 mass % orless, more preferably 30 mass % or less, further preferably 20 mass % orless, and specially further preferably 10 mass % or less relative to thetotal amount of the composition in terms of physical propertiesadjustment such as hardness and elongation of the cured material.

The aforementioned polymerization initiator is used mainly to improvethe initiation efficiency of polymerization reaction which progresses byirradiation of an active energy ray such as ultraviolet ray and electronray. As a polymerization initiator, an optical radical polymerizationinitiator which is a compound which produces a radical by the light, iscommon, and any known optical radical polymerization initiator isallowed as long as an effect of the present invention can be obtained.The optical radical polymerization initiator may be one type or two ormore types. The optical radical polymerization initiator can be usedwith a photosensitization agent.

An optical radical polymerization initiator includes benzophenone,2,4,6-trimethyl benzophenone, 4,4-bis(diethylamino) benzophenone,4-phenyl benzophenone, methylorthobenzoyl benzoate, thioxanthone,diethylthioxanthone, isopropyl thioxanthone, chlorothioxanthone, 2-ethylanthraquinone, t-butyl anthraquinone, diethoxy acetophenone,2-hydroxy-2-methyl-1-phenylpropane-1-on, benzyl dimethylketal, 1-hydroxycyclohexylphenyl ketone, benzoin methyl ether, benzoin ethyl ether,benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoyl formate,2-methyl-1-{4-(methylthio)phenyl}-2-morpholinopropane-1-on,2,6-dimethylbenzoyl diphenyl phosphine oxide, 2,4,6-trimethylbenzoyldiphenyl phosphine oxide,bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentyl phosphine oxide,bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-on,for example.

Among them, benzophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-on,1-hydroxy cyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide and2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-onare preferred and 1-hydroxy cyclohexylphenyl ketone,2,4,6-trimethylbenzoyl diphenyl phosphine oxide and2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl}-2-methyl-propane-1-onare preferred because its curing speed is high and its crosslinkingdensity can be elevated enough.

When the active-energy radiation curable polymer composition contains aradical polymerization group as well as cation polymerization group suchas epoxy group, the above optical radical polymerization initiator andan optical cation polymerization initiator may be included as apolymerization initiator. Any known optical cation polymerizationinitiator can also be used as long as an effect of the present inventioncan be obtained.

In an active-energy radiation curable polymer composition related to thesecond aspect of the present invention, the amount of these opticalpolymerization initiators is preferably 10 parts by mass or less andmore preferably 5 parts by mass or less, relative to the total amount of100 parts by mass of the aforementioned active energy ray reactivecomponents. When the amount of the optical polymerization initiator is10 parts by mass or less, decrease in mechanical strength due todegradation products of the initiator can be suppressed, which ispreferred.

The aforementioned photosensitization agent can be used for the samepurpose as the polymerization initiator. One type or two or more typesof photosensitization agents can be used and any knownphotosensitization agent can be used as far as effects of the presentinvention can be obtained. Such a photosensitization agent includesethanol amine, diethanol amine, triethanol amine, N-methyl diethanolamine, 4-dimethyl aminobenzoic acid methyl, 4-dimethyl aminobenzoic acidethyl, 4-dimethyl aminobenzoic acid amyl, and 4-dimethylaminoacetophenone, for example.

In an active-energy radiation curable polymer composition related to thesecond aspect of the present invention, the amount of the aforementionedphotosensitization agent is preferably 10 mass parts by mass or less andmore preferably 5 parts by mass or less, relative to the total amount of100 parts by mass of the aforementioned active energy ray reactivecomponents. When the amount of the photosensitization agent is 10 partsby mass or less, decrease in mechanical strength due to lowercrosslinking density can be suppressed, which is preferred.

For the aforementioned addition agent, various kinds of materials to beadded to a composition used for the similar application can be used asan addition agent as far as effects of the present invention can beobtained. The addition agent may be one type or two or more types. Suchan addition agent includes fillers such as glass fiber, glass beads,silica, alumina, calcium carbonate, isinglass, zinc oxide, titaniumoxide, mica, talc, kaolin, metallic oxide, metallic fiber, iron, lead,and metallic powder; carbon materials such as carbon fiber, carbonblack, black lead, carbon nanotube, and fullerenes such as C60 (fillersand carbon materials may be generically called “inorganic components”);modifying agents such as oxidation inhibitor, thermal stabilizer,ultraviolet absorber, HALS, fingerprint-resistant agent, surfacehydrophilic agent, antistatic agent, slippage imparting agent,plasticizing agent, mold release agent, antifoaming agent, levelingagent, antisettling agent, surfactant, thixotropy imparting agent,lubricant, flame retardant, flame retardant aid agent, polymerizationinhibitor, bulking agent, and silane coupling agent; coloring agentssuch as pigment, dye compound, and hue adjuster; monomer, and/or itsoligomer, or curative agent, catalyst, and curing accelerators which arenecessary for synthesizing an inorganic component.

In the active-energy radiation curable polymer composition related tothe second aspect of the present invention, the amount of theaforementioned addition agent is preferably 10 parts by mass or less andmore preferably 5 parts by mass or less, relative to the total amount of100 parts by mass of the aforementioned active energy ray reactivecomponents. When the amount of the addition agent is 10 parts by mass orless, decrease in mechanical strength due to lower crosslinking densitycan be suppressed, which is preferred.

The aforementioned solvent, for example, according to a coating methodfor forming a coating film of an active-energy radiation curable polymercomposition related to the second aspect of the present invention, canbe used in order to adjust viscosity of the active-energy radiationcurable polymer composition related to the second aspect of the presentinvention. One type or two or more types of solvents can be used and anyknown solvent can be used as far as effects of the present invention canbe obtained. Preferable solvents include toluene, xylene, ethyl acetate,butyl acetate, isopropanol, isobutanol, cyclohexane, methylethylketone,and methylisobutylketone. 400 parts by mass or less of the solvent canbe usually used to 100 parts by mass of an active-energy radiationcurable polymer composition.

A method for containing an optional ingredient such as theaforementioned addition agent to the active-energy radiation curablepolymer composition related to the second aspect of the presentinvention is not specifically limited, but conventionally known mixingand dispersion method can be provided. In order to disperse theaforementioned optional ingredients surely, a dispersion process using adispersion device is preferred. Specifically, for example, processingmethod using double-roll, triple roll, bead mill, ball mill, sand mill,pebble mill, trommel, sand grinder, segment barrier tryter,sun-and-planet stirring machine, high-speed impeller disperser,high-speed stone mill, high-speed impact mill, kneader, homogenizer, andultrasonic disperser, etc. can be included.

The viscosity of the active-energy radiation curable polymer compositionrelated to the second aspect of the present invention can be adjusted asrequired according to an application and usage aspect of thecomposition, while the viscosity of an E-type viscometer (rotor1°34′×R24) at 25° C. is preferably 10 mPa·s or more, more preferably 100mPa·s or more, while 100,000 mPa·s or less is preferable, and morepreferably 50,000 mPa·s or less in terms of handling, coating, formingand 3D molding. The viscosity of the active-energy radiation curablepolymer composition can be adjusted by, for example, the content of anurethane(meth)acrylate oligomer, a type of the aforementioned optionalingredient, and its blending ratio, etc.

As a coating method of the aforementioned active-energy radiationcurable polymer composition, an known method such as bar coater method,application method, curtain flow coater method, roll coater method,spray method, gravure coater method, comma coater method, reverse rollcoater method, lip coater method, die coater method, slot die coatermethod, air knife coater method, and dip coater method, etc. can beapplied, while the bar coater method and the gravure coater method arepreferred.

The active-energy radiation curable polymer composition related to thesecond aspect of the present invention can be a cured film byirradiating an active energy ray thereto.

An active energy ray to be used for curing the above compositionincludes infrared ray, visible ray, ultraviolet ray, X-ray, electronray, α-ray, β-ray, and γ-ray, etc. Electron ray or ultraviolet ray ispreferred in terms of an equipment cost and productivity, while as anlight source, electron irradiation equipment, extra high pressuremercury lamp, high pressure mercury lamp, middle pressure mercury lamp,low pressure mercury lamp, metal halide lamp, Ar laser, He—Cd laser,solid-state laser, xenon lamp, high-frequency induction mercury lamp, orsun light, etc. is suited.

The irradiance level of the active energy ray can be arbitrarilyselected according to the active-energy ray type, when it is cured byelectron ray irradiation, the irradiance level is preferred to be 1 to10 Mrad, for example. In case of ultraviolet ray irradiation, 50 to1,000 mJ/cm² is preferred. An atmosphere during curing may be an air oran inert gas such as nitrogen or argon. Irradiation in an enclosed spacebetween a film, glass and a metallic mold can also be applied.

The film thickness of the cured film related to the second aspect of thepresent invention can be arbitrarily decided according to a targetapplication, but the lower limit is preferably 1 μm, more preferably 3μm, and especially preferably 5 μm. Its upper limit is preferably 200μm, more preferably 100 μm, especially preferably 50 μm, and the mostpreferably 20 μm. When the film thickness is larger than 1 μm, itsdesign and functionality excellently appear after its 3D processing,while when it is smaller than 200 μm, an internal curing ability and 3Dprocessing suitability is excellent, which is preferred.

Furthermore, a laminated body having a layer consisting of a cured filmrelated to the second aspect of the present invention can be obtained ona base material. The laminated body related to the second aspect of thepresent invention is not specifically limited unless it has a layerconsisting of a cured film related to the second aspect of the presentinvention, and a layer other than the base material and the cured filmrelated to the second aspect of the present invention can be placedbetween the base material and the cured film related to the secondaspect of the present invention, or can be placed outside. Theaforementioned laminated body may have a base material and a pluralityof cured film layers related to the second aspect of the presentinvention.

As a method for obtaining a laminated body related to the second aspectof the present invention, any known method such as method of laminatingall layers when they are not cured and then curing them by an activeenergy ray, method of curing or partially-coating a lower layer by anactive energy ray, applying an upper layer, and then curing them againby an active energy ray, and method of applying each layer onto arelease film or a base film and then pasting those layers when they arenot cured or partially cured, can be applied, while method of curing byan active energy ray when they are not cured is preferred, in terms ofhigher adhesiveness between layers. As a laminating method without beingcured, an known method such as sequential application of applying alower layer and then overlapping an upper layer, and a simultaneousmultiple layer application of applying two or more layers at the sametime from a multiple-slit, can be applied, but not limited.

The base material includes polyester such as polyethylene terephthalateand polybutylene terephthalate, polyolefin such as polypropylene, andvarious kinds of plastic materials such as nylon, polycarbonate,(meth)acrylate resin, etc., or various shapes of goods such as plateformed by metal.

The cured film related to the second aspect of the present invention canbe a film excellent in contamination resistance and hardness against ageneral domestic contamination object such as ink and ethanol, etc.,while the laminated body related to the second aspect of the presentinvention in which the cured film related to the second aspect of thepresent invention is used as a film for various kinds of base materialscan be a one excellent in design and its surface protection.

The active-energy radiation curable polymer composition related to thesecond aspect of the present invention can give the cured film havingflexibility which can be followed during 3D processing transformation,elongation at break, mechanical strength, contamination resistance andhardness together by considering the molecular weight between calculatednetwork crosslinking points.

A value of the elongation at break of the cured film related to thesecond aspect of the present invention, in which the cured film relatedto the second aspect of the present invention is cut by 10 mm wide, atensile testing was done by using a Tensilon tensile tester (made byOrientec, co. ltd, Tensilon UIM-III-100) under conditions of temperatureof 140° C., tensile speed 50 mm/min., and the distance between chucks of50 mm, is preferably 50% or more, more preferably 75% or more, furtherpreferably 100% or more, and specially preferably 150% or more.

A value of the strength at break of a cured film related to the secondaspect of the present invention, in which the cured film related to thesecond aspect of the present invention is cut by 10 mm wide, a tensiletesting was done by using a Tensilon tensile tester (made by Orientec,co. ltd, Tensilon UTM-III-100) under conditions of temperature of 23°C., tensile speed 50 mm/min., and the distance between chucks of 50 mm,is preferably 40 MPa or more, more preferably 50 MPa or more, andfurther preferably 60 MPa or more.

A value of the elasticity of a cured film related to the second aspectof the present invention, in which the cured film related to the secondaspect of the present invention is cut by 10 mm wide, a tensile testingwas done by using a Tensilon tensile tester (made by Orientec, co. ltd,Tensilon UIM-III-100) under conditions of temperature of 23° C., tensilespeed 50 mm/min., and the distance between chucks of 50 mm, ispreferably 100 MPa or more, more preferably 200 MPa or more, furtherpreferably 500 MPa or more, specially preferably 1,000 MPa or more, andspecially preferably 2,000 MPa or more.

An value of the pencil hardness of the cured film related to the secondaspect of the present invention, which was tested by an abrasion tester(made by Shinto Scientific Co., Ltd.: Haydon Dynamic strain amplifier3K-34B) with a pencil of hardness 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H(made by Mitsubishi Pencil, Co. Ltd.; Product number UNI, inspected byJapan Pant Inspection and Testing Association, for pencil scratch test)under conditions of 23° C./53% RH at 1 Kgf (9.8 N) load at scratchingspeed 25 mm/min. for pulling by 1 cm, is preferably HB or higher, morepreferably F or higher, and further preferably H or higher.

Contamination resistance of the cured film related to the second aspectof the present invention is evaluated visually by dropping 0.03 g of 75mass % ethanol precipitation, a red water-based ink (a cartridge inkmade by Pilot Corporation/red/IRF-12S-R) or a blue water-based ink (acartridge ink made by Pilot Corporation/blue-black/IRF-12S-BB)(hereinafter, may be generally referred as “contaminated object”) tocontact the cured film, leave it at a room temperature (23° C.) for onehour for 75 mass % ethanol precipitation, while for 24 hours for a redor a blue water-based ink respectively, then wiping off the contaminatedobject by an absorbent cotton containing water. Where, the contaminatedobject amount after wiping it out is preferred to be an extremely smallamount, and further preferred to be too little to be apparent visually.

The cured film related to the second aspect of the present invention andthe laminated body related to the second aspect of the present inventioncan be used as an alternative film for paint, and can be effectivelyapplied to a building material for interior and exterior decorating aswell as various kinds of members such as automobile and homeelectronics.

As for the active-energy radiation curable polymer composition relatedto the second aspect of the present invention, when the cured film isobtained by curing it, contamination resistance against a generaldomestic contaminated object such as ink and ethanol, etc., and thecured film excellent in hardness can be obtained, and by using the curedfilm as a film for various kinds of base materials, the design and itssurface protection can be obtained.

The active-energy radiation curable polymer composition related to thesecond aspect of the present invention can give a cured film havingflexibility which can be followed during 3D processing transformation,elongation at break, mechanical strength, contamination resistance andhardness together by considering the calculated crosslinking pointsmolecular weight. The active-energy radiation curable polymercomposition related to the second aspect of the present invention isexpected to be able to easily produce a thin film resin sheet by onelayer application.

EXAMPLES

Hereinafter, the present invention is further described by usingexamples and comparative examples, but the present invention is notlimited to these embodiments unless it exceeds the argument.

Hereinafter, evaluation methods for values of respective physicalproperties are as follows.

[Evaluation Method: Polycarbonate Diol] [Number Average MolecularWeight]

The number average molecular weight (Mn) is calculated by solving aproduct into a CDCl₃ and measuring ¹H-NMR (AVANCE 400 made by BRUKER) at400 MHz to obtain its value of integral.

[Molecular Weight Distribution Mw/Mn]

The molecular weight distribution is calculated by obtaining Mn and Mwvalues on the conversion of polystyrene by measuring GPC under thefollowing conditions.

Equipment: Tosoh 8020 made by Tosoh Corporation.Column: PLgel 3 um MIXED-E (7.5 mmI.D.×30 cmL×2 columns)Eluting solution: THF (tetrahydrofuran)Current speed: 0.5 mL/min.Column temperature: 40° C.RI detector: RI (Equipment Tosoh 8020, built-in)

[Terminal Phenoxide Amount, Ether Bond Amount, Raw Material Diol Amount,and Phenol Amount]

They are calculated by solving a product into a CDCl₃ and measuring 400MHz ¹H-NMR (AVANCE 400 made by BRUKER) to obtain its integral value ofsignal of each component. The detection limit for this is 200 ppm asterminal phenoxide amount against the total weight of the entiresamples, 500 ppm as ether group weight, and 100 ppm for phenol, 0.1weight % for isosorbide, and 200 ppm for o-dichrolo benzene as a weightof a raw material diols or phenols. The terminal phenoxide proportion iscalculated from the ratio of an integrated value of one proton for anterminal phenoxide and an integrated value of one proton for the entireterminal (total of three structures of molecular chain terminalstructure (A), molecular chain terminal structure (B) and terminalphenoxide), while the detection limit for the terminal phenoxide againstthe entire terminal is 0.05%.

[Remaining Diester Carbonate Amount]

The remaining amount of diester carbonate (diphenyl carbonate) wasmeasured by GPC quantitative analysis under the following conditions:

(Analytical Conditions)

Column: Tskgel G2000 H XL 7.8 mm I.D×30 cm L 4 columnsEluting solution: THF (tetrahydrofuran)Current speed: 1.0 mL/min.Column temperature: 40° C.RI detector: RID-10A (Shimadzu Corporation)

[(A)/(B) Ratio, Terminal (A)/(B) Ratio, Terminal (A) Ratio (I)]

They are calculated by solving a product into CDCl₃ and measuring 400MHz ¹H-NMR (AVANCE400 made by BRUKER) to obtain its integral value. Itscalculation method is described below.

Each ratio is obtained from the following chemical shift value ofintegral on the NMR chart. The chemical shift value may slightly differaccording to its composition, in which case the value of integral needsto be arbitrarily obtained differently.

δ5.22 to 4.98 ppm value of integral=aδ4.79 to 4.61 ppm value of integral=bδ4.61 to 4.47 ppm value of integral=cδ3.68 to 3.51 ppm value of integral=dδ2.73 to 2.66 ppm value of integral=eδ1.52 to 1.30 ppm value of integral=f

Structure (A) of a molecular chain terminal contains two types ofisomers, which is classified as “(A) Terminal 1“and” (A) Terminal 2”respectively. A structure part derived from (A) in the polycarbonatediol other than the terminal is classified “(A) Intermediate” Similarly,(B) is classified as “(B) Terminal“and” (B) Intermediate”. Consideringthe respective number of protons, each number is calculated by thefollowing formula.

(A) Terminal 1=b−e

(A) Intermediate=c−(A) Terminal 1

(A) Terminal 2−a−(A) Terminal 1−(A) Intermediate×2

(B) Terminal=(d−e−(A) Terminal 1)/2

(B) Intermediate=(f−(B) Terminal×4)/4

The number of each structure formula in a molecular chain described informula (I) is represented as follows;

The number of molecular chain terminal structure (A)=(A) Terminal 1+(A)Terminal 2

The total number of molecular chain terminal structures (A) and (B)=(A)Terminal 1+(A) Terminal 2+(B) Terminal

The number of structures (A) in a molecular chain=(A) Terminal 1+(A)Terminal 2+(A) Intermediate

The total number of structures (A) and (B) in a molecular chain=(A)Terminal 1+(A) Terminal 2+(A) Intermediate+(B) Terminal+(B) Intermediate

Terminal (A) ratio (I) can be obtained by applying the above values toformula (I).

[APHA Value]

According to JIS K0071-1, it was compared and measured with a referencesolution stored in a color comparison tube.

[Viscosity]

After a product was heated to 50° C., measurement was made by usingE-type viscometer (DV-II+PRO made by BROOKFIELD, cone: CPE-52).

[Hydroxyl Value]

The value was measured and calculated by the following method. 14 g ofphthalic anhydride was solved into 100 mL of pyridine to prepare aphthalate reagent. 1.50 to 1.60 g of the polycarbonate diol is solvedinto 5 mL of this phthalate reagent to react for one hour at 100° C.After this reaction solution is cooled at room temperature, it wasdiluted with 25 mL mixed solvent of THF/H₂O (75/25). This solvent wastitrated by using 1 N aqueous sodium hydroxide to obtain the amount ofthe aqueous sodium hydroxide which has been used until a flexion pointis detected (main test). The same titration (blank test) was conductedfor a solvent in which 5 mL of the phthalate reagent was diluted with a25 mL mixed solvent of THF/H₂O (75/25).

The hydroxyl value was obtained by the amount of the obtained aqueoussodium hydroxide by using the following formula. The number averagemolecular weight was calculated from this hydroxyl value.

Hydroxyl value(mg−KOH/g)={56.1×(B−A)×f}/S  [Mathematical formula 4]

A: Volume of the 1N aqueous sodium hydroxide required for titrimetricdetermination in main test (mL)B: Volume of the 1N aqueous sodium hydroxide required for titrimetricdetermination in blank test (mL)f: Titre of 1N aqueous sodium hydroxide

S: Sample (g) [Average Number of Hydroxyl Groups Per Molecule]

The value was obtained by the following formula.

Average number of hydroxyl groups per molecule={(Number averagemolecular weight)×(Hydroxyl value)}/{1000×(KOH molecular weight)}

For the number average molecular weight, a measurement value of theaforementioned ¹H-NMR was used, while a calculated value at theaforementioned titration was used for a hydroxyl value.

[Catalyst Amount]

About 0.1 g of a polycarbonate diol product was measured and solved into4 mL of acetonitrile. Then 20 mL of pure water is added to precipitatethe polycarbonate diol and remove the precipitated polycarbonate diol byfiltration. Then the filtrated solvent is diluted to a predeterminedconcentration by pure water to analyze its metallic ion concentration byion chromatography analysis. Here, the metallic ion concentration of theacetonitrile to be used as a solvent was measured as a blank value,while a value of the metallic ion concentration for the solvent issubtracted to obtain the metallic ion concentration for thepolycarbonate diol product.

Measurement conditions are indicated in the following Table 1. Magnesiumion concentration was obtained by using results of analysis and thestandard curves which was prepared in advance.

TABLE 1 Cation Analyzer Dionex Japan [DX-320] Chromatopac: ShimadzuCorporation [C-R7A] Separation column IonPac CS12A Guard column IonPacCG12A Flow rate 1.0 mL/min Injection amount 1.5 mL Pressure 960-990 psiOVEN TEMP 35° C. Detection range RANGE 200 μS of detecter SuppressorCSRS current value: 60 mA Eluting solution Methanesulfonic acid 20mmol/L Retention time 10.9 min

[Evaluation Method: Polyurethane] [Molecular Weight]

GPC equipment made by Shimadze Corporation (Column TSKgel SuperHZM-N,lithium bromide-added dimethylacetamide for a solvent) is used to obtainthe number average molecular weight in terms of standard polystyrene(Mn) as a molecular weight.

[Film Tension Property]

A tensile elongation at break and 100% modulus were measured with astrip polyurethane sample of 10 mm wide, 100 mm long, and about 100 μmthick by using a tensile tester (made by Orientec, co. ltd, TensilonRTC-1210A) according to JIS K6301. It was executed under conditions ofthe distance between chucks of 50 mm, a tensile speed of 500 mm/min., atemperature of 23° C. and a relative humidity of 55

[Film Creep Property]

A polyurethane film with 100 μm thick is prepared, cut into a 10 mm-widestrip, marked reference line every 50 mm to obtain a sample. 1 MPa loadwas applied to this sample in a longitudinal direction under constanttemperature and humidity conditions of temperature 23° C. and relativehumidity 55% RH, and the load was removed after 16 hours later. Thelength of the reference line (Lmm) was measured to obtain its creepproperty ((L−50)/50)×100(%).

[Film Scratch Hardness (Pencil Method)]

A 100 μm-thick polyurethane was prepared and carefully attached andfixed onto a metallic mirror surface so as not to contain air bubble tomeasure its value according to JIS K-5600-5-4.

[Film Friction Resistant Test]

A 100 μm-thick polyurethane was prepared and fixed onto a tester(II-type, Gakushin-Type) to conduct up to 500 reciprocations of frictionresistance test under 4.9N load according to JIS L0849.

[Urethanization Speed Test]

The reactivity of urethanization of obtained polycarbonate diol wasobserved as follows. PCD was dissolved in N,N-dimethylformamide(hereinafter “DMF”) and added 0.98 times of diphenylmethane diisocyanate(hereinafter “MDI”) at a predetermined temperature against a molequivalent amount of the added polycarbonate diol, which was estimatedfrom OH value of the polycarbonate diol. Then, a load value (torque)which was a change of a churning motor load (unit: V) when the agitationof the solution was maintained at 100 rpm, was obtained. The read torquewas a value in which the value before MDI addition was subtracted. Forthe motor, an agitator MAZERA Z-1210 made by TOKYO RIKAKIKAI CO. Ltd.,was used. A 500 mL-separable flask was used as a polymerization reactor,and four wings combining two anchor types were used as agitation wings.Reactors, etc. to be used were well-washed and dried, and carefullyplaced so as not to contact air during a series of operations as much aspossible under conditions of nitrogen circulation or encapsulation. Adetection limit of the motor load value was 5 V. When the motor loadvalue exceeded about 2 V, a polymerization solution viscosity was toohigh, while the polymerization solution did not return to its originalstate by gravity after agitation wing shearing and free spinningpartially occurred, which did not result in correct motor load valuemeasurement.

[Evaluation Method: Urethane(meth)acrylate Oligomer] [Calculation Methodof the Number Average Molecular Weight]

The urethane(meth)acrylate oligomer of examples and referenceexperiments contain three types of components of polyisocyanate,polycarbonate diol and hydroxyalkyl(meth)acrylate as its structuralunits. These structural units were formed with their component molecularweights maintained in the urethane(meth)acrylate oligomer, so in theexamples and reference experiments, the average molecular weight of theurethane(meth)acrylate oligomer is calculated by total of products ofthose component mol ratios and molecular weights until theurethane(meth)acrylate oligomer is generated.

[Measurement of the Number Average Molecular Weight by GPC]

By using GPC (“HLC-8120 GPC” made by TOSOH Corporation), THF as asolvent, polystyrene as a standard sample, and TSKgelsuperH1000+H2000+H3000 as a column, the number average molecular weightof the urethane(meth)acrylate oligomer was measured at solution sendingspeed at 0.5 mL/min. and the column oven temperature of 40° C.

[Calculation of the Calculated Crosslinking Points Molecular Weight]

Since reactive group for a hydroxyalkyl(meth)acrylate in an urethaneacrylate oligomer prepolymer is isocyanate group at both terminals ofthe prepolymer, and hydroxyalkyl(meth)acrylate bound to both terminalsof the prepolymer by urethane bond is added by radical polymerization,so the crosslinking points of the urethane acrylate oligomer in thecomposition is(meth)acryloyl group located at both terminals of theurethane(meth)acrylate oligomer.

Therefore the active-energy radiation curable polymer composition is anaforementioned bifunctional (multifunctional) compound-single systemcomposition in the following examples and reference experiments. Thus,the calculated crosslinking points molecular weight in those examplesand reference experiments were obtained by the following formula.

(Number average molecular weight of the urethane(meth)acrylateoligomer/Number of cross-linking point in the urethane(meth)acrylateoligomer)×2  [Mathematical formula 5]

[Viscosity]

By using 1.2 g of an active-energy radiation curable polymercomposition, a viscosity was measured by E-type viscometer (“TVE-20H”made by TOKYO KEIKI Inc.) with settings of rotation range 10 rpm, rotor1°34′×R24, at 25° C.

[Mechanical Property of a Cured Film]

A cured film was cut by 10 mm wide, tensile testing was done by using aTensilon tensile tester (made by Orientec, co. ltd, TensilonUTM-III-100) under conditions of temperature of 23° C., relativehumidity 53%, tensile speed 50 mm/min., and the distance between chucksof 50 mm to measure elongation at break, strength at break and tensileelasticity.

[Contamination Resistance of Cured Film]

0.03 g of a black oil-based ink, a red oil-based ink, a blue water-basedink (a cartridge ink made by Pilot Corporation/blue-black/IRF-12S-BB), ared water-based ink (a cartridge ink made by PilotCorporation/red/IRF-12S-R), 10 mass % HCl aqueous solution, or 10 mass %NaOH aqueous solution (hereinafter, generally referred as “contaminatedobject”) was dropped to contact a cured film, left it at a roomtemperature (23° C.) for 24 hours respectively, then wiped off thecontaminated object by an absorbent cotton containing IPA for the blackoil-based ink and the red oil-based ink, by an absorbent cottoncontaining water for the blue water-based ink, the red water-based ink,the 10 mass % HCl aqueous solution, or the 10 mass % NaOH aqueoussolution to visually evaluate its contamination. Evaluation standard wasas follows;

∘: Contaminated object can be completely wiped out.Δ: Small amount of contaminated object remains.x: Substantial amount of contaminated object remains.

[Pencil Hardness of a Cured Film]

The hardness was tested by an abrasion tester (made by Shinto ScientificCo., Ltd.: Haydon Dynamic strain amplifier 3K-34B) with a pencil ofhardness 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H (made by Mitsubishi Pencil,Co. Ltd.; Product number UNI, inspected by Japan Pant Inspection andTesting Association, for pencil scratch test) under conditions of 23°C./53% RH. A 6B pencil of hardness was attached to the abrasion testerand pulled by 1 cm at 1 Kgf (9.8 N) load at scratching speed 25 mm/min.to visually check if any pulling evidence could be recognized or not.When any pulling evidence was not found, the pencil was replaced withone more level harder, and then repeated the similar operation to findout the hardest pencil hardness of which evidence was not found.

Experimental Example 1-1

1,6-hexanediol: 195.9 g, isosorbide: 242.3 g, diphenyl carbonate: 658.2g, and magnesium acetate tetrahydrate: 4.3 mg were put into a 1 L glassseparable flask, which was equipped with an agitator, a distillationtrap, and a pressure adjusting device, and nitrogen gas replacement wasconducted. The content was heated to 160° C. at its internal temperaturefor dissolution and for one-hour reaction. Then, the pressure wasreduced down to 0.27 kPa gradually in two hours to distill and removephenol and unreacted diol during the reaction. Then, nitrogen gasbubbling was conducted at 180° C. and 2.7 kPa for 45 minutes to distilland remove phenol and unreacted diol during the reaction. 400 g ofo-dichrolobenzene was added and the pressure was maintained at 0.27 kPaand 130° C. for 2 hours for reaction, then bubbling with nitrogen gaswas conducted for 2 hours at 2.7 kPa to remove the phenol and raise itspolymerization degree of polycarbonate diol. The obtained polycarbonatediol product was 488.8 g.

The number average molecular weight (Mn) obtained from the hydroxylvalue of the polycarbonate diol contained in this polycarbonate diolproduct was 1,940, the molecular weight distribution (Mw/Mn) was 1.96,(A)/(B) ratio (isosorbide/1,6-hexanediol) was 49/51, Terminal (A)/(B)ratio (terminal isosorbide/1,6-hexanediol ratio) was 73/27, and theterminal (A) ratio (I) calculated by the aforementioned (I) was 1.46.

The property of obtained polycarbonate diol product was a transparentsolid at room temperature. The amount of raw diol isosorbide was 0.6weight %, the phenol amount was 0.02 weight %, while the phenoxideterminal was 2% of entire terminals, and any polymer containing an etherbond other than isosorbide skeleton and o-dichrolobenzene was notdetected. Remaining diphenyl carbonate was lower than the quantitationlimit (lower than 0.01 weight %).

Experimental Example 2-1

1,6-hexanediol: 293.9 g, isosorbide: 121.2 g, diphenyl carbonate: 658.2g, and magnesium acetate tetrahydrate: 4.3 mg into a 1 L glass separableflask, which was equipped with an agitator, a distillation trap, and apressure adjusting device, and nitrogen gas replacement was conducted.The content was heated to 160° C. at its internal temperature fordissolution and for one-hour reaction. Then, the pressure was reduceddown to 0.27 kPa gradually in two hours to distill and remove phenol andunreacted diol during the reaction. Then, nitrogen gas bubbling wasconducted at 180° C. and 2.7 kPa for 15 minutes to distill and removephenol and unreacted diol during the reaction. 400 g ofo-dichrolobenzene was added and the pressure was maintained at 0.27 kPaand 130° C. for 5 hours for reaction, then bubbling with nitrogen gaswas conducted for 13 hours at 2.7 kPa to remove the phenol and raise itspolymerization degree of polycarbonate diol. The obtained polycarbonatediol product was 454.2 g.

The number average molecular weight (Mn) obtained from the hydroxylvalue of the polycarbonate diol contained in this polycarbonate diolproduct was 2,100, the molecular weight distribution (Mw/Mn) was 1.96,(A)/(B) ratio was 24/76, Terminal (A)/(B) ratio was 62/38, and Terminal(A) ratio (I) was 2.58.

The property of obtained polycarbonate diol product was viscous liquidat a room temperature and fluidity was recognized. Viscosity (50° C.)was 24 Pa·s. The amount of raw diol isosorbide was 0.5 weight %, and apolymer which became a phenoxide terminal, a polymer containing an etherbond other than isosorbide skeleton, phenol and o-dichrolobenzene wasnot detected. Remaining diphenyl carbonate was lower than thequantitation limit (lower than 0.01 weight %).

Experimental Example 3-1

1,6-hexanediol: 218.5 g, isosorbide: 264.4 g, a diphenyl carbonate:620.0 g, and magnesium acetate tetrahydrate: 4.7 mg were put into a 1 Lglass separable flask, which was equipped with an agitator, adistillation trap, and a pressure adjusting device, and nitrogen gasreplacement was conducted. The content was heated to 160° C. at itsinternal temperature for dissolution and for one-hour reaction. Then,the pressure was reduced down to 0.27 kPa gradually in two hours todistill and remove phenol and unreacted diol during the reaction. Thenbubbling with nitrogen gas was conducted for 1.5 hours at 160° C. and0.27 kPa to remove the phenol and unreacted diol. Then bubbling wasconducted for 4 hours at 110° C. with the pressure kept at 0.27 kPa toremove the phenol. The obtained polycarbonate diol product was 520.5 g.

The number average molecular weight (Mn) obtained from the hydroxylvalue of the polycarbonate diol contained in this polycarbonate diolproduct was 880, (A)/(B) ratio (isosorbide/1,6-hexanediol) was 49/51,Terminal (A)/(B) ratio (terminal isosorbide/1,6-hexanediol ratio) was60/40, and the terminal (A) ratio (I) calculated by the aforementioned(I) was 1.22.

The property of obtained polycarbonate diol product was a transparentsolid at room temperature. The amount of raw diol isosorbide was 2.0weight %, phenol amount was 0.06 weight %, and a polymer which became aphenoxide terminal and a polymer containing an ether bond other thanisosorbide skeleton were not detected. Remaining diphenyl carbonate waslower than the quantitation limit (lower than 0.01 weight %).

Experimental Example 4-1

1,6-hexanediol: 202.4 g, isosorbide: 750.9 g, diphenyl carbonate: 1046.8g, and an aqueous solution of magnesium acetate tetrahydrate: 8.7 mL(concentration: 8.4 g/L, magnesium acetate tetrahydrate: 73 mg) were putinto 5 L glass separable flask, which was equipped with an agitator, adistillation trap, and a pressure adjusting device, and nitrogen gasreplacement was conducted. The content was firstly heated to 130° C. atits internal temperature for dissolution. When it was heated anddissolved, the pressure was reduced down to 5.33 kPa in 5 min. to reactit for 240 min. at 5.33 kPa by distilling and removing the phenol. Thenthe pressure was reduced down to 0.40 kPa in 120 min., and then thetemperature was raised to 160° C. in 80 min. to react it whiledistilling and removing the phenol and unreacted diol. Finally, thephenol and unreacted diol was distilled and removed at 0.40 kPa for 40min. at 160° C. The obtained polycarbonate diol product was 989.2 g.

A thin-film distilling was conducted for the obtained polycarbonate diolproduct at flow rate of 20 g/min. (temperature: 180 to 200° C.,Pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained from the hydroxylvalue of the polycarbonate diol contained in this polycarbonate diolproduct after this thin-film distilling was 900, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 76/24, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 91/9, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 1.20.

The property of obtained polycarbonate diol product after this thin-filmdistilling was a light-yellow solid at room temperature. The amount ofraw diol isosorbide was 2.5 weight %, and the phenol, a polymer whichbecame a phenoxide terminal and a polymer containing an ether bond otherthan isosorbide skeleton were not detected. Remaining diphenyl carbonatewas lower than the quantitation limit (lower than 0.01 weight %).

Experimental Example 1-2

78.3 g of the polycarbonate diol which was produced at Experimentalexample 1-1 was preheated to a melting point (ex. 120° C.) or more andadded to a 1 L separable flask, the flask was placed in an oil bath setat 55° C. to heat and dimethylformamide (DMF) was added to dissolve it.An agitation started at about 100 rpm, 1,4-butanediol: 3.6 g was added,and tin stearate: 0.014 g was dropped. Then diphenylmethane diisocyanate(MDI): 19.8 g was dropped at a speed in which the liquid temperaturedoes not exceed 70° C. MDI was dropped little by little up to 2.6 guntil the weight-average molecular weight exceeds 150,000 measured byGPC to obtain a polyurethane solution of which solid concentration was30 weight %. This polyurethane solution was applied onto a polyethylenefilm at uniform film thickness by a doctor blade and dried by a drier toobtain a polyurethane film.

When physical properties of this film were measured, its tensileelongation at break was 215% and 100% modulus was 53 MPa. The creepproperty of this film was 2%, a scratch hardness (Pencil method) was 2Bto B, a friction resistant test returns no special surface differenceafter 500 reciprocations, and the weight reduction ratio was 1%.

Experimental Example 2-2

In stead of the polycarbonate diol made at Experimental example 1-1, thepolycarbonate diol which was made at Experimental example 2-1 was usedand others are the same as Experimental example 1-2 for reaction toobtain a polyurethane of which solid concentration was 30 weight %. Thispolyurethane solution was applied onto a polyethylene film at uniformfilm thickness by a doctor blade and dried by a drier to obtain apolyurethane film.

When physical properties of this film were measured, its tensileelongation at break was 324% and 100% modulus was 13 MPa. The creepproperty of this film was 15%, a scratch hardness (Pencil method) was6B, scratch on its surface was recognized. A friction resistant testreturns no special surface difference after 500 reciprocations, and theweight reduction ratio was 0.3%.

Reference Experimental Example 1-2

In stead of the polycarbonate diol made at Experimental example 1-1, apolycarbonate diol (Duranol T6002, the number average molecular weight:1,986, made by Asahi Kasei Chemicals Corporation): 523 g was used andothers are the same as Experimental example 1-2 for reaction to obtain apolyurethane of which solid concentration was 30 weight %. Thispolyurethane solution was applied onto a polyethylene film at uniformfilm thickness by a doctor blade and dried by a drier to obtain apolyurethane film.

When these film physical properties were measured, its tensileelongation at break was 580% and 100% modulus was 2.6 MPa. The creepproperty of this film was 6%, a scratch hardness (Pencil method) was 6B,and a substantial scratch on its surface was recognized. At a frictionresistance test, substantial damage was recognized on its surface after100 reciprocations, and the test had to be stopped.

[Consideration of Polyurethane Film]

Table 2 indicates physical properties of the polycarbonate diol productobtained at the aforementioned Experimental examples 1-1 and 2-1, andphysical properties of the polyurethane film obtained by using thosepolycarbonate diol products at the aforementioned Experimental examples1-2 and 2-2.

TABLE 2 Comparative Example 1 Example 2 example 1 Experimental exampleNo./ Experimental Experimental Reference experimental example exampleexample No. 1-1 2-1 — Raw 16 HD 50 75 — material ISB 50 25 — diol [mol%] Physical Molecular 1940 2100 — property of weight poly- (OH value)carbonate Aspect Transparent Viscous — diol solid liquid Experimentalexample Experimental Experimental Reference No./Reference experimentalexample example experimental example No. 1-2 2-2 example 1-2 PhysicalTensile fracture 215 324 580 property of elongation Poly- [%] urethane100% modulus 53 13 2.6 film [MPa] Creep property 2 15 6 [%] Pencilhardness 2B-B 6 B 6 B

As is clear from Examples 1 and 2, the polyurethane film created by thepolycarbonate dial obtained by using isosorbide and 1,6-hexanediol as araw material diol indicates a high 100% modulus and a high frictionresistance is indicated at a friction resistance test that the surfaceis nearly unchanged after 500 reciprocations. In particular, Example 1with high ISB ratio indicates a high pencil hardness of 2B to B.

On the other hand, as is clear from Comparative example 1, thepolyurethane film produced by the polycarbonate diol obtained by using1,6-hexanediol only as a raw material diol indicates lower strength andhardness than the polycarbonate diol produced by isosorbide and at afriction resistance test, substantial damage was recognized on itssurface after 100 reciprocations, and the test had to be stopped.

Experimental Example 1-3

To a four-outlet flask equipped with an agitator, a reflux condenser, adrip funnel, and a thermometer, 119 g of isophorone diisocyanate as apolyisocyanate, and 519 g of the polycarbonate diol of Experimentalexample 1-1 as an polycarbonate diol and 273 g of methylethylketone wereadded and reaction was conducted by heating to 80° C. in an oil bath for9 hours. After the reaction, it was cooled down to 60° C.; then 0.21 gof dioctyltin dilaurate, 0.35 g of methylhydroquinone, and 27 g ofmethylethylketone were added; and 62 g of hydroxyethyl acrylate as ahydroxyalkyl(meth)acrylate was dropped to start reaction. Reaction wasexecuted for 10 hours while heating at 70° C. in an oil bath to checkthe reaction progress with the decrease of peak derived from isocyanate(NCO) group by Infrared absorption spectrum (may be abbreviated as IR),while its reaction's ending point was confirmed at its disappearance toobtain urethane(meth)acrylate oligomer 1. The urethane(meth)acrylateoligomer 1 solution obtained by this was an active-energy radiationcurable polymer composition 1.

The obtained active-energy radiation curable polymer composition 1 had acalculated crosslinking points molecular weight of 2,620. Theurethane(meth)acrylate oligomer 1 obtained by GPC had the number averagemolecular weight of 2,570. Moreover, the amount of theurethane(meth)acrylate oligomer 1 in the active-energy radiation curablepolymer composition 1 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition 1 was 2,260 mPa·s.

Next, the obtained active-energy radiation curable polymer composition 1was coated onto a polyethylene terephthalate film by an applicator toform a coated film, dried it for one minute at 60° C., an electronirradiation apparatus (CB175, EYE GRAPHICS CO., LTD.) was used toirradiate an electron beam onto the dried coated film under thecondition of accelerating voltage of 165 kV and exposure dose of 5 Mradto form a cured film 1. Then, the cured film 1 is delaminated from thepolyethylene terephthalate film to obtain the cured film 1 with the filmthickness of 50 μm.

Mechanical properties, contamination resistance, abrasion resistance andpencil hardness were evaluated about the obtained cured film 1. Theirresults are shown in Table 3.

Experimental Example 2-3

Although isophorone diisocyanate was changed from 119 g to 112 g, the519 g of polycarbonate diol of Experimental example 1-1 is changed tothe 530 g of polycarbonate diol of Experimental example 2-1,methylethylketone was changed from 273 g to 275 g, methylethylketone waschanged from 27 g to 25 g, hydroxyethyl acrylate was from 62 g to 59 g,other conditions were the same as Experimental example 1-3 to obtain anurethane(meth)acrylate oligomer 2 as well as an active-energy radiationcurable polymer composition 2, which was an urethane(meth)acrylateoligomer 2 solution.

The obtained active-energy radiation curable polymer composition 2 had amolecular weight between calculated network cross-linking points of2,780. The urethane(meth)acrylate oligomer 2 obtained by the GPC had thenumber average molecular weight of 2, 870. The amount of theurethane(meth)acrylate oligomer 2 in the active-energy radiation curablepolymer composition 2 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition 2 was 2,720 mPa·s.

Then, except for using the active-energy radiation curable polymercomposition 2 obtained in the above, its conditions were the same asExperimental example 1-3 to obtain a cured film 2. Mechanicalproperties, contamination resistance, abrasion resistance and pencilhardness were evaluated about the obtained cured film 2. Their resultsare shown in Table 3.

Experimental Example 3-3

Isophorone diisocyanate was changed from 119 g to 200 g, 519 g of thepolycarbonate diol at Experimental example 1-1 was changed to 396 g ofthe polycarbonate diol at Experimental example 3-1, a methylethylketonewas from 273 g to 255 g, a methylethylketone was increased from 27 g to45 g, a hydroxyethyl acrylate was from 62 g to 104 g, but otherconditions were the same as Experimental example 1-3 to obtain anurethane(meth)acrylate oligomer 3 as well as an active-energy radiationcurable polymer composition 3 which was an urethane(meth)acrylateoligomer 3 solution.

The obtained active-energy radiation curable polymer composition 3 had amolecular weight between calculated network cross-linking points of1,550. Moreover, the urethane(meth)acrylate oligomer 3 obtained by GPChad the number average molecular weight of 1, 690. The amount of theurethane(meth)acrylate oligomer 3 in the active-energy radiation curablepolymer composition 3 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition 3 was 1,190 mPa·s.

Then, except for using the active-energy radiation curable polymercomposition 3 obtained in the above, its conditions were the same asExperimental example 1-3 to obtain a cured film 3. Mechanicalproperties, contamination resistance, abrasion resistance and pencilhardness were evaluated about the obtained cured film 3. Their resultsare shown in Table 3.

Experimental Example 4-3

Isophorone diisocyanate was changed from 119 g to 197 g, 519 g of thepolycarbonate diol at Experimental example 1-1 was changed to 400 g ofthe polycarbonate diol at Experimental example 4-1, methylethylketonewas from 273 g to 256 g, methylethylketone was from 27 g to 44 g,hydroxyethyl acrylate was from 62 g to 103 g, but other conditions werethe same as Experimental example 1-3 to obtain an urethane(meth)acrylateoligomer 4 as well as an active-energy radiation curable polymercomposition 4 which was an urethane(meth)acrylate oligomer 4 solution.

The obtained active-energy radiation curable polymer composition 4 had amolecular weight between calculated network cross-linking points of1,570. The urethane(meth)acrylate oligomer 4 obtained by the GPC had thenumber average molecular weight of 1, 670. The amount of theurethane(meth)acrylate oligomer 4 in the active-energy radiation curablepolymer composition 4 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition 4 was 9,540 mPa·s.

Then, except for using the active-energy radiation curable polymercomposition 4 obtained in the above, its conditions were the same asExperimental example 1-3 to obtain a cured film 4. Mechanicalproperties, contamination resistance, abrasion resistance and pencilhardness were evaluated about the obtained cured film 4. Their resultsare shown in Table 3.

Reference Experimental Example 2-3

Isophorone diisocyanate was changed from 119 g to 116 g, 519 g of thepolycarbonate diol at Experimental example 1-1 was changed to 523 g ofthe polycarbonate diol (Duranol T 5652, number average molecular weight:2,000, made by Asahi Kasei Chemicals Corporation), methylethylketone tobe added before the pre-polymer generation reaction was from 273 g to274 g, methylethylketone to be added after the pre-polymer generationreaction was from 27 g to 26 g, hydroxyethyl acrylate was from 62 g to61 g, but other conditions were the same as Experimental example 1-3 toobtain an urethane(meth)acrylate oligomer C1 as well as an active-energyradiation curable polymer composition C1 which was anurethane(meth)acrylate oligomer C1 solution.

The obtained active-energy radiation curable polymer composition C1 hada molecular weight between calculated network cross-linking points of2,680. The urethane(meth)acrylate oligomer C1 obtained by GPC had thenumber average molecular weight of 2,870. The amount of theurethane(meth)acrylate oligomer C1 in the active-energy radiationcurable polymer composition C1 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition 1 was 1,390 mPa·s.

Then, except for using the active-energy radiation curable polymercomposition C1 obtained in the above, its conditions were the same asExperimental example 1-3 to obtain a cured film C1. Mechanicalproperties, contamination resistance, abrasion resistance and pencilhardness were evaluated about the obtained cured film C1. Their resultsare shown in Table 3.

Reference Experimental Example 3-3

Isophorone diisocyanate was changed from 119 g to 117 g, 519 g of thepolycarbonate diol at Experimental example 1-1 was changed to 523 g ofthe polycarbonate diol (Kuraray polyol C-2050, number average molecularweight: 1, 990, made by KURARAY CO., LTD.), methylethylketone to beadded before the prepolymer generation reaction was from 273 g to 274 g,methylethylketone to be added after the prepolymer generation reactionis from 27 g to 26 g, hydroxyethyl acrylate was from 62 g to 61 g, butother conditions were the same as Experimental example 1-3 to obtain anurethane(meth)acrylate oligomer C2 as well as an active-energy radiationcurable polymer composition C2 which was an urethane(meth)acrylateoligomer C2 solution.

The obtained active-energy radiation curable polymer composition C2 hada molecular weight between calculated network cross-linking points of2,670. The urethane(meth)acrylate oligomer C2 obtained by GPC had thenumber average molecular weight of 2,600. The amount of theurethane(meth)acrylate oligomer C2 in the active-energy radiationcurable polymer composition C2 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition C2 was 890 mPa·s.

Then, except for using the active-energy radiation curable polymercomposition C2 obtained in the above, its conditions were the same asExperimental example 1-3 to obtain a cured film C2. Mechanicalproperties, contamination resistance, abrasion resistance and pencilhardness were evaluated about the obtained cured film C2. Their resultsare shown in Table 3.

Reference Experimental Example 4-3

Isophorone diisocyanate was changed from 119 g to 115 g, 519 g of thepolycarbonate diol at Experimental example 1-1 was changed to 525 g ofthe polycarbonate diol (Nipporan 980N, number average molecular weight:2,030, made by NIPPON POLYURETHANE INDUSTRY CO., LTD.),methylethylketone to be added before the prepolymer generation reactionwas from 273 g to 274 g, methylethylketone to be added after theprepolymer generation reaction was from 27 g to 26 g, hydroxyethylacrylate was from 62 g to 60 g, but other conditions were the same asExperimental example 1-3 to obtain an urethane(meth)acrylate oligomer C3as well as an active-energy radiation curable polymer composition C3which was an urethane(meth)acrylate oligomer C3 solution.

The obtained active-energy radiation curable polymer composition C3 hada molecular weight between calculated network cross-linking points of2,710. The urethane(meth)acrylate oligomer C3 obtained by GPC had thenumber average molecular weight of 2,820. The amount of theurethane(meth)acrylate oligomer C3 in the active-energy radiationcurable polymer composition C3 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition C3 was 1560 mPa·s.

Then, except for using the active-energy radiation curable polymercomposition C3 obtained in the above, its conditions were the same asExperimental example 1-3 to obtain a cured film C3. Mechanicalproperties, contamination resistance, abrasion resistance and pencilhardness were evaluated about the obtained cured film C3. Their resultsare shown in Table 3.

Reference Experimental Example 5-3

Isophorone diisocyanate was changed from 119 g to 195 g, 519 g of thepolycarbonate diol at Experimental example 1-1 was changed to 404 g ofthe polycarbonate diol (ETERNACOL UM-90 (1/1), number average molecularweight: 920, made by Ube Industries, Ltd.), methylethylketone to beadded before the prepolymer generation reaction was from 273 g to 256 g,methylethylketone to be added after the prepolymer generation reactionwas from 27 g to 44 g, hydroxyethyl acrylate was from 62 g to 102 g, butother conditions were the same as Experimental example 1-3 to obtain anurethane(meth)acrylate oligomer C4 as well as an active-energy radiationcurable polymer composition C4 which was an urethane(meth)acrylateoligomer C4 solution.

The obtained active-energy radiation curable polymer composition had amolecular weight between calculated network cross-linking points of1,600. The urethane(meth)acrylate oligomer C4 obtained by GPC had thenumber average molecular weight of 1, 840. The amount of theurethane(meth)acrylate oligomer C4 in the active-energy radiationcurable polymer composition C4 was 70 mass %, and the viscosity of theactive-energy radiation curable polymer composition C4 was 750 mPa·s.

Then, except for using the active-energy radiation curable polymercomposition C4 obtained in the above, its conditions were the same asExperimental example 1-3 to obtain a cured film C4. Mechanicalproperties, contamination resistance, abrasion resistance and pencilhardness were evaluated about the obtained cured film C4. Their resultsare shown in Table 3.

TABLE 3 Reference Reference Reference Reference ExperimentalExperimental Experimental Experimental experimental experimentalexperimental experimental example example example example exampleexample example example 1-3 2-3 3-3 4-3 2-3 3-3 4-3 5-3 Urethane a-1Isophorone diisocyanate (number average molecular weignt 222) 119 112200 197 116 117 115 195 acrylate a-2 Experimental example 1-1(polycarbonate polyol) 519 oligomer (calculated with the number averagemolecular weight 1940/OH [Weight ratio] number 57.82) Experimentalexample 2-1 (polycarbonate polyol) 530 (calculated with the numberaverage molecular weight 2100/OH number 53.5) Experimental example 3-1(polycarbonate polyol) 396 calculated with the number average molecularweight 880/OH number 127) Experimental example 4-1 (polycarbonatepolyol) 400 (calculated with the number average molecular weight 900/OHnumber 125) a-3 Hydroxyethyl acrylate (number average molecular weight116) 62 59 104 103 61 61 60 102 a-4 T5652 (polycarbonate polyol) 523(calculated with the number average molecular weight 2000/OH number 56.1(analyzed value provided by the manufacturer) C-2050 (polycarbonatepolyol) 523 (calculated with the number average molecular weight 1990/OHnumber 56.5 (analyzed value provided by the manufacturer) 980N(polycarbonate diol) 525 (calculated with the number average molecularweight 2030/OH number 554 (analyzed value provided by the manufacturer)UM-90(1/1) (polycarbonate diol) 404 (calculated with the number averagemolecular weight 920/OH number 122.7 (analyzed value provided by themanufacturer) Urethane a-1 Isophorone diisocyanate (number averagemolecular weight 222) 2 2 2 2 2 2 2 2 acrylate a-2 Experimental example1-1 (polycarbonate polyol) 1 oligomer (calculated with the numberaverage molecular weight 1940/OH [Mol ratio] number 57.82) Experimentalexample 2-1 (polycarbonate polyol) 1 (calculated with the number averagemolecular weight 2100/OH number 53.5) Experimental example 3-1(polycarbonate polyol) 1 (calculated with the number average molecularweight 880/OH number 127) Experimental example 4-1 (polycarbonatepolyol) 1 (calculated with the number average molecular weight 900/OHnumber 125) a-3 Hydroxyethyl acrylate (number average molecular weight116) 2 2 2 2 2 2 2 2 a-4 T5652 (polycarbonate polyol) 1 (calculated withthe number average molecular weight 2000/OH number 56.1 (analyzed valueprovided by the manufacturer) C-2050 (polycarbonate polyol) 1(calculated with the number average molecular weight 1990/OH number 56.5(analyzed value provided by the manufacturer) 980N (polycarbonate diol)1 (calculated with the number average molecular weight 2030/OH number55.4 (analyzed value provided by the manufacturer) UM-90(1/1)(polycarbonate diol) 1 (calculated with the number average molecularweight 920/OH number 122.7 (analyzed value provided by the manufacturer)Urethane The calculated-number average molecular weight 2620 2780 15501570 2680 2670 2710 1600 acrylate The number average molecular weightmesured by GPC 2570 2870 1690 1670 2870 2600 2820 1840 oligomer Activeenergy Content of urethane(meth)acrylate oligomer [mass %] 70 70 70 7070 70 70 70 ray-curable Viscosity [mPa · s/25 degrees C.) 2260 2720 11909540 1390 890 1560 750 polymer Calculated molecular weight betweencrosslinking points 2620 2780 1550 1570 2680 2670 2710 1600 compositionCured film Mechanical Tensile fracture 110 150 5 5 110 90 120 60properties elongation [%] Tensile fracture strength 60 60 50 60 10 10 2030 [MPa] Tensile elasticity [MPa] 2020 140 2010 2110 10 12 10 100Contamination Black oil-based ink (r.t.x left as it is for 24 Hrs, thenwiped x x ∘ ∘ x x x Δ resistance off with IPA) Red oil-based ink (r.t.xleft as it is for 24 Hrs, then wiped x Δ ∘ ∘ x x x Δ off with IPA) Bluewater-based ink (r.t.x left with cover for 24 Hrs, then Δ x ∘ ∘ x x x Δwiped off with a damp cloth) Red water-based ink (r.t.x left with coverfor 24 Hrs, then ∘ x ∘ ∘ x x x Δ wiped off with a damp cloth) 10 wt %HCl aqueous (r.t.x left with cover for 24 Hrs, then ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘solution wiped off with a damp cloth) 10 wt % NaOH aqueous (r.t.x leftwith cover for 24 Hrs, then ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ solution wiped off with adamp cloth) Pencil hardness HB 3B H H 5B 3B 6B F

Constitutional unit mass ratio of a polyol in a polycarbonate polyol, OHvalue of a polyol in a polycarbonate polyol, and the number averagemolecular weight of a polyol in a polycarbonate polyol are indicated inTable 4. The number average molecular weights of T5652, C-2050, 980N andUM-90 (1/1) are values in their brochures.

TABLE 4 Experi- Experi- Experi- Experi- Reference Reference ReferenceReference mental mental mental mental experimental experimentalexperimental experimental example example example example exampleexample example example 1-3 2-3 3-3 4-3 2-3 3-3 4-3 5-3 Polycarbonatepolyol Isosorbide 50 25 50 75 0 0 0 0 Constitutional unit:Cyclohexanedimethanol 0 0 0 0 0 0 0 50 Raw material glycol1,5-Pentanediol 0 0 0 0 50 0 0 0 [Weight ratio] 3- Methylpentanediol 0 00 0 0 50 0 0 1,6-Hexanediol 50 75 50 25 50 50 100 50 OH value [mgKOH/g]57.52 53.5 127.7 125 56.1 56.5 55.4 122.7 Number average molecularweight 1940 2100 880 900 2000 1990 2030 920 The average number ofhydroxyl 2.0 2.0 2.0 2.0 2.0 2.0 2.0 2.0 groups per one molecule

[Consideration of a Cured Film]

Table 5 indicates physical properties of the polycarbonate diol productsobtained at the aforementioned Experimental examples 1-1, 2-1, 3-1, and4-1 and physical properties of the polyurethane films obtained by usingthose polycarbonate diol products at the aforementioned Experimentalexamples 1-2, 2-2, 3-2 and 4-2.

TABLE 5 Comparative Comparative Comparative Comparative Example 3Example 4 Example 5 Example 6 example 2 example 3 example 4 example 5Experimental example Experimental Experimental Experimental Experimental— — — — No./Reference example 1-1 example 2-1 example 3-1 example 4-1experimental example No. Raw material 16 HD 50 75 50 25 — — — — diol ISB50 25 50 75 — — — — [mol %] Physical Molecular 1940 2100 880 900 — — — —property of weight polycarbonate (OH value) diol Average 2.0 2.0 2.0 2.0— — — — number of hydroxyl groups per one molecule Aspect TransparentViscous Transparent Light-yellow — — — — solid liquid solid solid WhiteNone None None None — — — — foreign body Experimental exampleExperimental Experimental Experimental Experimental Reference ReferenceReference Reference No./Reference example 1-1 example 2-3 example 3-3example 4-3 experimental experimental experimental experimentalexperimental example No. example 2-3 example 3-3 example 4-3 example 5-3Cured film Tensile 110 150 5 5 110 90 120 60 properties fractureelongation [%] Tensile 60 60 50 60 10 10 20 30 fracture strength [MPa]Tensile 2020 140 2010 2110 10 12 10 100 elasticity [MPa] Pencil HB 3B HH 5B 3B 6B F hardness

Polycarbonate polyol in Example 3, Comparative example 2, andComparative example 3 all have almost the same number average molecularweight, calculated molecular weight between cross-linking points, and OHvalues, and 50 mass % of constitutional units are 1,6-hexanediol, whileremaining 50 mass % of the constitutional unit in Example 3 areisosorbide, but 1,5-pentanediol and 3-methylpentane diol in Comparativeexample 2 and 3. The cured film in Example 3 has an almost same tensileelongation at break as cured films in Reference experiments example 2-3and 3-3, better tensile strength at break, more higher contaminationresistance against a water-based ink, and higher pencil hardnessrelative to these Reference experiments.

Polycarbonate polyol in Example 4 and Comparative example 4 all havealmost the same number average molecular weight, calculated molecularweight between cross-linking points, and OH values, and 75 mass % ofconstitutional units are 1,6-hexanediol in Example 4 and remaining 25mass % are isosorbide, but in Comparative example 4, all constitutionalunits are 1,6-hexanediol. The cured film in Example 4 has better tensileelongation at break than the cured film in Comparative example 4, bettertensile strength at break, higher contamination resistance against a redoil-based ink, and higher pencil hardness relative to the comparativeexample.

Polycarbonate polyol in Example 5 and Comparative example 5 all havealmost the same number average molecular weight, calculated molecularweight between cross-linking points, and OH values, and 50 mass % ofconstitutional units are 1,6-hexanediol, while in Example 5 theremaining 50 mass % are isosorbide, but in Comparative example 5, iscyclohexane dimethanol. The cured film in Example 5 has lower tensileelongation at break however it has higher tensile strength at breakcompared to the cured film in Comparative example 5, and it has highercontamination resistance against a water-based and oil-based ink, andhigher pencil hardness relative to the comparative example.

Polycarbonate polyol in Examples 6 and 5 all have almost the same numberaverage molecular weight, calculated molecular weight betweencross-linking points, and OH values, while a proportion of isosorbide ina constitutional unit consisting of 1,6-hexanediol and isosorbide is 75mass % in Example 6, but 50 mass % in Example 5. The cured film inExample 6 has almost the same tensile strength at break andcontamination resistance, and pencil hardness compared to the cured filmin Example 5.

In this regard, when a cured film, which was obtained from anactive-energy radiation curable polymer composition containing anurethane(meth)acrylate oligomer is used, in which the oligomer was giventenderization trend by including a high-molecular weight polyol havingover 500 number average molecular weights excluding the aforementionedpolycarbonate diol thereto, and/or increasing calculated molecularweight between cross-linking points thereof etc., the cured filmcontaining polycarbonate diol of Experimental example 4-1 is estimatedto be better balanced between 3D processing characteristic andcontamination resistance compared to the cured film containing thepolycarbonate diol at Experimental example 3-1.

From the aforementioned examples and comparative examples, it is clearthat the composition containing polycarbonate polyol containingisosorbide in its constitutional unit and having cross-linking points atboth terminals can form a better cured film by irradiating an activeenergy ray excellent in mechanical strength and contamination resistancethan a similar composition containing other polycarbonate polyol.

Experimental Example 5-1

1,6-hexanediol (16 HD): 404.3 g, isosorbide (ISB): 500.1 g, diphenylcarbonate: 1095.6 g, and an aqueous solution of magnesium acetatetetrahydrate: 0.87 mL (concentration: 8.4 g/L, magnesium acetatetetrahydrate: 7.3 mg) were put into a 5 L glass separable flask, whichwas equipped with an agitator, a distillation trap, and a pressureadjusting device, and nitrogen gas replacement was conducted. Thecontent was firstly heated to 130° C. at its internal temperature fordissolution. When it was heated and dissolved, the pressure was reduceddown to 4.67 kPa in 5 min. to react it at 130° C. for 20 min. at 4.67kPa. Then the pressure was reduced down to 0.40 kPa in 260 min., andthen the temperature was raised to 160° C. in 80 min. to react it whiledistilling and removing the phenol and unreacted diol. The obtainedpolycarbonate diol product was 805.0 g. The contained magnesium amountwas 1.06 weight ppm.

A thin-film distilling was conducted for the obtained polycarbonate diolproduct at flow rate of 20 g/min. (temperature: 180 to 200° C.,Pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained after this thin-filmdistilling from NMR analysis of the polycarbonate diol contained in thispolycarbonate diol product was 1, 465, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 61/39, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 68/32, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 1.11.

The property of obtained polycarbonate diol product was a transparentsolid at a room temperature and the contained magnesium amount was 1.14weight ppm. APHA value was 60, and the amount of raw diol isosorbide was0.14 weight %, phenol amount was 0.23 weight %, and the phenoxideterminal was 9% of entire terminals. Any polymer containing an etherbond other than isosorbide skeleton was not detected. Remaining diphenylcarbonate was lower than the quantitation limit (lower than 0.01 weight%).

Experimental Example 6-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g; diphenyl carbonate: 1095.6g; and an aqueous solution of magnesium acetate tetrahydrate: 4.4 mL(concentration: 8.4 g/L, magnesium acetate tetrahydrate: 37 mg) were putinto a 5 L glass separable flask, which was equipped with an agitator, adistillation trap, and a pressure adjusting device, and nitrogen gasreplacement was conducted. The content was firstly heated to 130° C. atits internal temperature for dissolution. When it was heated anddissolved, the pressure was reduced down to 5.33 kPa in 5 min. to reactit at 130° C. for 180 min. at 5.33 kPa by distilling and removing thephenol. Then the pressure was reduced down to 0.40 kPa in 100 min., andthen the temperature was raised to 160° C. in 100 min. to react whiledistilling and removing the phenol and unreacted diol. The obtainedpolycarbonate diol product was 967.8 g. The contained magnesium amountwas 4.29 weight ppm.

The number average molecular weight (Mn) obtained from NMR analysis ofthe polycarbonate diol contained in this polycarbonate diol product was928, (A)/(B) ratio (isosorbide/1,6-hexanediol) was 51/49, Terminal(A)/(B) ratio (terminal isosorbide/1,6-hexanediol ratio) was 71/29, andthe terminal (A) ratio (I) calculated by the aforementioned (I) was1.39.

The property of obtained polycarbonate diol product was a transparentsolid at room temperature. APHA value was 60, and the amount of raw diolisosorbide was 3.60 weight %, phenol amount was 1.06 weight %, and apolymer which became a phenoxide terminal and a polymer containing anether bond other than isosorbide skeleton were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Experimental Example 7-1

1,6-hexanediol: 404.3, isosorbide: 500.1 g; diphenyl carbonate: 1095.6g; and an aqueous solution of magnesium acetate tetrahydrate: 8.7 mL(concentration: 8.4 g/L, magnesium acetate tetrahydrate: 73 mg) were putinto a 5 L glass separable flask, which was equipped with an agitator, adistillation trap, and a pressure adjusting device, and nitrogen gasreplacement was conducted. The content was firstly heated to 130° C. atits internal temperature for dissolution. When it was heated anddissolved, the pressure was reduced down to 5.33 kPa in 5 min. to reactit at 130° C. for 180 min. at 5.33 kPa by distilling and removing thephenol. Then the pressure was reduced down to 0.40 kPa in 120 min., andthen the temperature was raised to 160° C. in 70 min. to react it whiledistilling and removing the phenol and unreacted diol. The obtainedpolycarbonate diol product was 970.0 g. The contained magnesium amountwas 9.35 weight ppm.

Moreover, a thin-film distilling was conducted for the obtainedpolycarbonate diol product at flow rate of 20 g/min. (temperature: 180to 200° C., pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained after this thin-filmdistilling from NMR analysis of the polycarbonate diol contained in thispolycarbonate diol product was 980, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 50/50, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 70/30, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 1.40.

The property of obtained polycarbonate diol product was a transparentsolid at a room temperature and the contained magnesium amount was 9.97weight ppm. APHA value was 60, and the amount of raw diol isosorbide was0.60 weight %, phenol amount was 0.04 weight %, and a polymer whichbecame a phenoxide terminal and a polymer containing an ether bond otherthan isosorbide skeleton were not detected. Remaining diphenyl carbonatewas lower than the quantitation limit (lower than 0.01 weight %).

Experimental Example 8-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and an aqueous solution of magnesium acetate tetrahydrate: 17.5 mL(concentration: 8.4 g/L, magnesium acetate tetrahydrate: 147 mg) wereput into a 5 L glass separable flask, which was equipped with anagitator, a distillation trap, and a pressure adjusting device, andnitrogen gas replacement was conducted. The content was firstly heatedto 130° C. at its internal temperature for dissolution. When it washeated and dissolved, the pressure was reduced down to 5.33 kPa in 5min. to react it at 130° C. for 150 min. at 5.33 kPa by distilling andremoving the phenol. Then the pressure was reduced down to 0.40 kPa in110 min., and then the temperature was raised to 160° C. in 60 min. toreact it while distilling and removing the phenol and unreacted diol.The obtained polycarbonate diol product was 972.5 g. The containedmagnesium amount was 17.5 weight ppm.

The number average molecular weight (Mn) obtained from NMR analysis ofthe polycarbonate diol contained in this polycarbonate diol product was924, (A)/(B) ratio (isosorbide/1,6-hexanediol) was 50/50, Terminal(A)/(B) ratio (terminal isosorbide/1,6-hexanediol ratio) was 70/30, andthe terminal (A) ratio (I) calculated by the aforementioned (I) was1.40.

The property of obtained polycarbonate diol product was a transparentsolid at room temperature. APHA value was 60, and the amount of raw diolisosorbide was 3.91 weight %, phenol amount was 1.17 weight %, and apolymer which became a phenoxide terminal and a polymer containing anether bond other than isosorbide skeleton were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Experimental Example 9-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and an aqueous solution of magnesium acetate tetrahydrate: 8.7 mL(concentration: 50.4 g/L, magnesium acetate tetrahydrate: 440 mg) wereput into a 5 L glass separable flask, which was equipped with anagitator, a distillation trap, and a pressure adjusting device, andnitrogen gas replacement was conducted. The content was firstly heatedto 130° C. at its internal temperature for dissolution. When it washeated and dissolved, the pressure was reduced down to 6.67 kPa in 5min. to react it at 130° C. for 150 min. at 6.67 kPa by distilling andremoving the phenol. Then the pressure was reduced down to 0.40 kPa in210 min., and then the temperature was raised to 160° C. in 100 min. toreact it while distilling and removing the phenol and unreacted diol.The obtained polycarbonate diol product was 987.0 g. The containedmagnesium amount was 65.9 weight ppm. The property of obtainedpolycarbonate diol product was a transparent solid at a room temperatureand contained a white Mg salt agglomerate.

A thin-film distilling was conducted for the obtained polycarbonate diolproduct at flow rate of 20 g/min. (temperature: 180 to 200° C.,Pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained after this thin-filmdistilling from NMR analysis of the polycarbonate diol contained in thispolycarbonate diol product was 1,067, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 46/54, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 85/15, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 1.85.

The property of obtained polycarbonate diol product after this thin-filmdistilling was a transparent solid at a room temperature and thecontained magnesium amount was 49.3 weight ppm. APHA value was 70, andthe amount of raw diol isosorbide was 1.66 weight %, and phenol, apolymer which became a phenoxide terminal and a polymer containing anether bond other than isosorbide skeleton were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Experimental Example 10-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and an aqueous solution of magnesium acetate tetrahydrate: 8.7 mL(concentration: 100.8 g/L, magnesium acetate tetrahydrate: 877 mg) wereput into a 5 L glass separable flask, which was equipped with anagitator, a distillation trap, and a pressure adjusting device, andnitrogen gas replacement was conducted. The content was firstly heatedto 130° C. at its internal temperature for dissolution. When it washeated and dissolved, the pressure was reduced down to 6.67 kPa in 5min. to react it at 130° C. for 150 min. at 6.67 kPa by distilling andremoving the phenol. Then the pressure was reduced down to 0.40 kPa in180 min., and then the temperature was raised to 160° C. in 100 min. todistill and remove the phenol and unreacted diol. The obtainedpolycarbonate diol product was 986.9 g. The obtained magnesium contentwas 113 weight ppm. The property of obtained polycarbonate diol productwas a transparent solid at a room temperature and contained a white Mgsalt agglomerate.

A thin-film distilling was conducted for the obtained polycarbonate diolproduct at flow rate of 20 g/min. (temperature: 180 to 200° C.,Pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained after this thin-filmdistilling from NMR analysis of the polycarbonate diol contained in thispolycarbonate diol product was 1,054, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 46/54, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 90/10, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 1.96.

The property of polycarbonate diol after this thin-film distilling was atransparent solid at a room temperature and the contained magnesiumamount was 104 weight ppm. APHA value was 60, and the amount of raw diolisosorbide was 1.47 weight %, and phenol, a polymer which becamephenoxide terminal and a polymer containing an ether bond other thanskeleton were not detected. Remaining diphenyl carbonate was lower thanthe quantitation limit (lower than 0.01 weight %).

Experimental Example 11-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and aqueous calcium acetate solution: 7.2 mL (concentration: 8.4 g/L,calcium acetate: 61 mg) were put into a 5 L glass separable flask, whichwas equipped with an agitator, a distillation fluid trap, and a pressureadjusting device, and nitrogen gas replacement was conducted. Thecontent was firstly heated to 130° C. at its internal temperature fordissolution. When it was heated and dissolved, the pressure was reduceddown to 4.67 kPa in 5 min. to react it at 130° C. for 140 min. at 4.67kPa by distilling and removing the phenol. Then the pressure was reduceddown to 0.40 kPa in 80 min., and then the temperature was raised to 160°C. in 120 min. to distill and remove the phenol and unreacted diol. Theobtained polycarbonate diol product was 926.4 g.

The number average molecular weight (Mn) obtained from NMR analysis ofthe polycarbonate diol contained in this polycarbonate diol product was1,130, (A)/(B) ratio (isosorbide/1,6-hexanediol) was 50/50, Terminal(A)/(B) ratio (terminal isosorbide/1,6-hexanediol ratio) was 92/8, andthe terminal (A) ratio (I) calculated by the aforementioned (I) was1.84.

The property of obtained polycarbonate diol product was a transparentsolid at room temperature. APHA value was 60, and the amount of raw diolisosorbide was 4.29 weight %, phenol amount was 0.23 weight %, and apolymer which became a phenoxide terminal and a polymer containing anether bond other than isosorbide skeleton were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Experimental Example 12-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and aqueous barium acetate solution: 10.4 mL (concentration: 8.4 g/L,barium acetate: 87 mg) were put into a 5 L glass separable flask, whichwas equipped with an agitator, a distillation trap, and a pressureadjusting device, and nitrogen gas replacement was conducted. Thecontent was firstly heated to 130° C. at its internal temperature fordissolution. When it was heated and dissolved, the pressure was reduceddown to 5.33 kPa in 5 min. to react it at 130° C. for 180 min. at 5.33kPa by distilling and removing the phenol. Then the pressure was reduceddown to 0.40 kPa in 100 min., and then the temperature was raised to160° C. in 80 min. to distill and remove the phenol and unreacted diol.The obtained polycarbonate diol product was 964.8 g.

The number average molecular weight (Mn) obtained from NMR analysis ofthe polycarbonate diol contained in this polycarbonate diol product was1,028, (A)/(B) ratio (isosorbide/1,6-hexanediol) was 48/52, Terminal(A)/(B) ratio (terminal isosorbide/1,6-hexanediol ratio) was 92/8, andthe terminal (A) ratio (I) calculated by the aforementioned (I) was1.92.

The property of obtained polycarbonate diol product was a transparentsolid at room temperature. APHA value was 60, and the amount of raw diolisosorbide was 5.68 weight %, phenol amount was 0.70 weight %, and apolymer which became a phenoxide terminal and a polymer containing anether bond other than isosorbide skeleton were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Experimental Example 13-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and sodium acetate: 3.3 mL (concentration: 8.4 g/L, sodium acetate:28 mg) were put into a 5 L glass separable flask, which was equippedwith an agitator, a distillation trap, and a pressure adjusting device,and nitrogen gas replacement was conducted. The content was firstlyheated to 130° C. at its internal temperature for dissolution. When itwas heated and dissolved, the pressure was reduced down to 5.33 kPa in 5min. to react it at 130° C. for 280 min. at 5.33 kPa by distilling andremoving the phenol. Then the pressure was reduced down to 0.40 kPa in240 min., and then the temperature was raised to 160° C. in 60 min. todistill and remove the phenol and unreacted diol at 0.40 kPa for 30 min.at 160° C. The obtained polycarbonate diol product was 957.0 g.

The number average molecular weight (Mn) obtained from NMR analysis ofthe polycarbonate diol contained in this polycarbonate diol product was1,053, (A)/(B) ratio (isosorbide/1,6-hexanediol) was 49/51, Terminal(A)/(B) ratio (terminal isosorbide/1,6-hexanediol ratio) was 90/10, andthe terminal (A) ratio (I) calculated by the aforementioned (I) was1.84.

The property of obtained polycarbonate diol product was a transparentsolid at room temperature. APHA value was 60, and the amount of raw diolisosorbide was 5.25 weight %, phenol amount was 0.43 weight %, and apolymer which became a phenoxide terminal and a polymer containing anether bond other than isosorbide skeleton were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Reference Experimental Example 6-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and an aqueous solution of magnesium acetate tetrahydrate solution:8.7 mL (concentration: 336.0 g/L, magnesium acetate tetrahydrate: 2,923mg) were put into a 5 L glass separable flask, which was equipped withan agitator, a distillation trap, and a pressure adjusting device, andnitrogen gas replacement was conducted. The content was firstly heatedto 130° C. at its internal temperature for dissolution. When it washeated and dissolved, the pressure was reduced down to 6.67 kPa in 5min. to react it at 130° C. for 190 min. at 5.33 to 8.00 kPa bydistilling and removing the phenol. Then the pressure was reduced downto 0.40 kPa in 100 min., and then the temperature was raised to 150° C.in 60 min. to distill and remove the phenol and unreacted diol. Theobtained polycarbonate diol product was 990.0 g. The obtained magnesiumcontent was 315 weight ppm. The property of obtained polycarbonate diolproduct was a transparent solid at a room temperature and contained awhite Mg salt agglomerate.

A thin-film distilling was conducted for the obtained polycarbonate diolproduct at flow rate of 20 g/min. (temperature: 180 to 200° C.,Pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained after this thin-filmdistilling from NMR analysis of the polycarbonate diol contained in thispolycarbonate diol product was 1,122, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 45/55, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 90/10, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 2.00.

The property of obtained polycarbonate diol product after this thin-filmdistilling was a transparent solid at a room temperature and thecontained magnesium amount was 350 weight ppm. APHA value was 70, andthe amount of raw diol isosorbide was 2.97 weight %, and phenol, apolymer which became a phenoxide terminal and a polymer containing anether bond other than isosorbide structure were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Reference Experimental Example 7-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and an aqueous solution of magnesium acetate tetrahydrate: 0.051 mL(concentration: 8.4 g/L, magnesium acetate tetrahydrate: 0.4 mg) into a5 L glass separable flask, which was equipped with an agitator, adistillation trap, and a pressure adjusting device, for nitrogen gasreplacement. The content was firstly heated to 130° C. at its internaltemperature for dissolution. When it was heated and dissolved, thepressure is reduced down to 6.67 kPa in 5 min. to react it at 130° C.for 100 min. at 6.67 kPa. Then the pressure was reduced down to 2.67 kPain 30 min. to react it at 2.67 kPa for 340 min. at 130° C. About 5 mLdistillated objects were found and little phenol generation wasrecognized in the system, therefore the reaction was stopped. A mixtureafter the reaction showed the almost the same weight as the added rawmaterial, so the contained Mg amount was considered to be 0.07 ppm(theoretical value).

Reference Experimental Example 8-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and an aqueous solution of magnesium acetate tetrahydrate: 8.7 mL(concentration: 8.4 g/L, magnesium acetate tetrahydrate: 73 mg) were putinto a 5 L glass separable flask, which was equipped with an agitator, adistillation trap, and a pressure adjusting device, and nitrogen gasdisplacement was conducted. The content is firstly heated to 130° C. atits internal temperature for dissolution. When it was heated anddissolved, the pressure was reduced down to 6.67 kPa in 5 min. to reactit at 130° C. for 240 min. at 5.33 to 6.67 kPa by distilling andremoving the phenol. Then the pressure was reduced down to 0.40 kPa in140 min., and then the temperature was raised to 180° C. in 60 min. todistill and remove the phenol and unreacted diol at 0.40 kPa for 280min. at 180° C. The property of the obtained polycarbonate diol productwas a transparent solid at room temperature, and its yield was 906.4 g.The contained magnesium amount was 9.43 weight ppm.

A thin-film distilling was conducted for the obtained polycarbonate diolproduct at flow rate of 20 g/min. (temperature: 180 to 200° C.,Pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained after this thin-filmdistilling from NMR analysis of the polycarbonate diol contained in thispolycarbonate diol product is 1,082, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 47/53, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 92/8, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 1.96.

The property of the obtained polycarbonate diol product after thisthin-film distilling was a transparent solid at a room temperature andthe contained magnesium amount was 9.97 ppm. APHA value was 100, and theamount of raw diol isosorbide was 1.08 weight %, and phenol, a polymerwhich became or a phenoxide terminal and a polymer containing an etherbond other than isosorbide structure were not detected. Remainingdiphenyl carbonate was lower than the quantitation limit (lower than0.01 weight %).

Reference Experimental Example 9-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and zinc acetate: 62.8 mg were put into a 5 L glass separable flask,which was equipped with an agitator, a distillation trap, and a pressureadjusting device, and nitrogen gas replacement was conducted. Thecontent was firstly heated to 130° C. at its internal temperature fordissolution. When it was dissolved, the pressure was reduced down to6.67 kPa in 5 min. to react it at 130° C. for 210 min. at 6.67 kPa bydistilling and removing the phenol. Then the pressure was reduced downto 0.40 kPa in 390 min., and then the temperature was raised to 160° C.in 90 min. to react it while distilling and removing the phenol at 0.40kPa for 50 min. at 160° C. The obtained polycarbonate diol product was943.4 g.

The number average molecular weight (Mn) obtained from NMR analysis ofthe polycarbonate diol contained in this polycarbonate diol product is1,021, (A)/(B) ratio (isosorbide/1,6-hexanediol) was 48/52, Terminal(A)/(B) ratio (terminal isosorbide/1,6-hexanediol ratio) was 85/15, andthe terminal (A) ratio (I) calculated by the aforementioned (I) was1.77.

The property of obtained polycarbonate diol product was a yellow solidwith white turbidity at room temperature. APHA could not be measured dueto white turbidity. The amount of raw diol isosorbide was 4.77 weight %,phenol amount was 0.41 weight %, and a polymer which became a phenoxideterminal and a polymer containing an ether bond other than isosorbideskeleton were not detected. Remaining diphenyl carbonate was lower thanthe quantitation limit (lower than 0.01 weight

Reference Experimental Example 10-1

1,6-hexanediol: 404.3 g, isosorbide: 500.1 g, diphenyl carbonate: 1095.6g, and zinc acetate: 345 mg were put into a 5 L glass separable flask,which was equipped with an agitator, a distillation trap, and a pressureadjusting device, and nitrogen gas replacement was conducted. Thecontent was firstly heated to 130° C. at its internal temperature fordissolution. When it was dissolved, the pressure was reduced down to6.67 kPa in 5 min. to react it at 130-140° C. for 330 min. at 6.67 kPaby distilling and removing the phenol. Then the temperature was raisedto 165° C. in 210 min. at the pressure of 4.67 to 8.67 kPa to distilland remove the phenol. Then the pressure was reduced down to 0.40 kPa in30 min. and the temperature was raised to 190° C. in 120 min. to distilland remove the phenol. The obtained polycarbonate diol product was 922.2g.

A thin-film distilling was conducted for the obtained polycarbonate diolproduct at flow rate of 20 g/min. (temperature: 180 to 200° C.,Pressure: 0.027 kPa).

The number average molecular weight (Mn) obtained after this thin-filmdistilling from NMR analysis of the polycarbonate diol contained in thispolycarbonate diol product was 1,088, (A)/(B) ratio(isosorbide/1,6-hexanediol) was 46/54, Terminal (A)/(B) ratio (terminalisosorbide/1,6-hexanediol ratio) was 93/7, and the terminal (A) ratio(I) calculated by the aforementioned (I) was 2.02.

The property of obtained polycarbonate diol product was a yellow solidwith white turbidity at room temperature. APHA could not be measured dueto white turbidity. The amount of raw diol isosorbide was 0.30 weight %,and phenol, a polymer which became phenoxide terminal and a polymercontaining an ether bond other than isosorbide structure were notdetected. Remaining diphenyl carbonate was lower than the quantitationlimit (lower than 0.01 weight %).

Experimental Example 5-4

95.6 g of the polycarbonate diol after thin-film distilling which wasobtained in the Experimental example 5-1 was preheated to a meltingpoint or higher (ex. 150° C.) and added to a separable flask, the flaskwas placed in an oil bath set at 50° C. to heat and 134 g of DMF wasadded to dissolve it. During agitation at 100 rpm, 14.0 g of MDI wasadded. Then an agitation torque's voltage value change due to increasein viscosity was read and the aspect of the content was observed.

In this case, it took very long time for polymerization, and its torquewas only 0.2 V even in one hour later. Even in four hours later, itsviscosity was increased little by little, but the torque was about 0.7V.

Experimental Example 7-4

85.0 g of the polycarbonate diol after thin-film distilling which wasobtained in the Experimental example 7-1 was preheated to a meltingpoint or higher (ex. 100° C.) and added to a separable flask, the flaskwas placed in an oil bath set at 50° C. to heat and 131 g of DMF wasadded to dissolve it. During agitation at 100 rpm, 21.9 g of MDI wasadded. Then an agitation torque's voltage value change due to increasein viscosity was read and the aspect of the content was observed.

In this case, it took about 42 min. to exceed the torque 1.0 V and theviscosity increase speed was easily-handled range. Then the viscosityslowly increased and the the increase stopped at the torque of about 1.7V.

Experimental Example 9-4

84.9 g of the polycarbonate diol after thin-film distilling which wasobtained in the Experimental example 9-1 was preheated to a meltingpoint or higher (ex. 100° C.) and added to a separable flask, the flaskwas placed in an oil bath set at 50° C. to heat and 131 g of DMF wasadded to dissolve it. During agitation at 100 rpm, 22.1 g of MDI wasadded. Then an agitation torque's voltage value change due to increasein viscosity was read and the aspect of the content was observed.

In this case, it took about 14 min. to exceed the torque 1.0 V and theviscosity increase speed was in an easily-handled range. Then theviscosity slowly increased and the increase stopped at the torque ofabout 1.8 V.

Experimental Example 10-4

85.0 g of the polycarbonate diol after thin-film distilling which wasobtained in the Experimental example 10-1 was preheated to a meltingpoint or higher (ex. 100° C.) and added to a separable flask, the flaskwas placed in an oil bath set at 50° C. to heat and 129 g of DMF wasadded to dissolve it. During agitation at 100 rpm, 20.9 g of MDI wasadded. Then an agitation torque's voltage value change due to increasein viscosity was read and the aspect of the content was observed.

In this case, a certain amount of gel was formed right after MDI beingadded, but as a whole this was an easy-handling polymerized solution. Ittook about 10 min. to exceed the torque 0.7 V and the viscosity increasespeed was in an easily-handled range.

However, the gel forming resulted in a heterogeneous solution and lowviscosity was partially recognized, so the torque did not exceed 1.0 V.

Reference Experimental Example 6-4

85.0 g of the polycarbonate diol after thin-film distilling which wasobtained in the Reference Experimental example 6-1 was preheated to amelting point or higher (ex. 100° C.) and added to a separable flask,the flask was placed in an oil bath set at 50° C. to heat and 132 g ofDMF was added to dissolve it. During agitation at 100 rpm, 22.8 g of MDIwas added. (Actual experiment was conducted at 50% solute. No resultchange was expected, so the solvent amount had been changed from 108 gto 45%.)

In this case, a great amount of gel was formed right after MDI addition,and almost all amount was stuck to an agitation wing to be like a ball.Therefore, measuring the viscosity increase speed was impossible.

Reference Experimental Example 8-4

85.0 g of the polycarbonate diol after thin-film distilling which wasobtained in the Reference Experimental example 8-1 was preheated to amelting point or higher (ex. 100° C.) and added to a separable flask,the flask was placed in an oil bath set at 50° C. to heat and 129 g ofDMF was added to dissolve it. During agitation at 100 rpm, 20.6 g of MDIwas added. Then an agitation torque's voltage value change due toincrease in viscosity was read and the aspect of the content wasobserved.

In this case, it took about 16 min. to exceed the torque 1.0 V, then inabout 19 min. later, the value reached 2.7 V, and then a surge wasrecognized and it became unmeasurable.

Reference Experimental Example 10-4

65.0 g of the polycarbonate diol after thin-film distilling which wasobtained in the Reference Experimental example 10-1 was preheated to amelting point or higher (ex. 100° C.) and added to a separable flask,the flask was placed in an oil bath set at 50° C. to heat and 146 g ofDMF was added to dissolve it. During agitation at 100 rpm, 13.7 g of MDIwas added. Then an agitation torque's voltage value change due toviscosity increase was read and an aspect of the content was observed(this was a condition for 35% solute). In this case, it took about 32min. to exceed the torque 1.0 V, and the viscosity increase speed was inan easily-handled range. Then the viscosity slowly increased and the theincrease stopped at the torque of about 1.7 V.

[Consideration of Amount of Catalyst and Urethanization Reaction Speed]

Tables 6 and 7 show summaries of the amount of the raw material diolwhich was used in producing the polycarbonate diol, types of catalyst,amount of catalyst, yield and reaction time, the catalyst amountcontained in a polycarbonate diol product, and whether acatalyst-derived metallic salt aggregate exists or not, and results ofurethanization reaction speed tests with a polycarbonate diol productbeing used, about the aforementioned Experimental examples 5-1 to 13-1,the aforementioned Reference Experimental examples 6-1, 7-1, 9-1 and10-1. In Tables 6 and 7, the amount of catalyst indicates aconcentration in a weight against the used diol amount. In Table 6, “*”indicates a theoretical value. In Tables 6 and 7, a parentheticalnumerical value about the amount of catalyst indicates a value beforethin-film distillation is done.

TABLE 6 Example 7 Example 8 Example 9 Example 10 Example 11 Experimentalexample No./Reference Experimental Experimental ExperimentalExperimental Experimental experimental example No. example 5-1 example6-1 example 7-1 example 8-1 example 9-1 Row materials 16 HD 50 50 50 5050 Diol ISB 50 50 50 50 50 [mol %] Catalyst Type Mg(OAc)₂•4H₂OMg(OAc)₂•4H₂O Mg(OAc)₂•4H₂O Mg(OAc)₂•4H₂O Mg(OAc)₂•4H₂O Used amount[ppm] 0.9 4.6 9.1 18.4 46 Reactivity Yield [%] 77.6 93.3 93.5 93.9 95.1Time [min] 454 427 416 373 502 Physical Contained amont of 1.14 — 9.97 —49.3 properties catalyst [ppm] (Before thin-film (1.06) (4.29) (9.35)(17.5) (65.9) distillation) Existence of None None None None Existsmetallic salt aggregates Experimental example No./Reference Experimental— Experimental — Experimental experimental example No. example 5-4example 7-4 example 9-4 Urethanization Time till 0.7 V [min] Approx. 240— 33 — 10 reaction rate Time till 1.0 V [min] — — 42 — 14 Load value at30 0.12 — 0.57 — 1.60 min [V] Load value at 60 min 0.21 — 1.50 — 1.80[V] Final load value [V] 0.70 — 1.70 — 1.80 Example 12 Example 13Example 14 Example 15 Experimental example No./Reference ExperimentalExperimental Experimental Reference experimental example No. example11-1 example 12-1 example 13-1 Experimental example 7-1 Row materials 16HD 50 50 50 50 Diol ISB 50 50 50 50 [mol %] Catalyst Type Ca(OAc)₂•H₂OBa(OAc)₂•H₂O NaOAc Mg(OAc)₂•4H₂O Used amount [ppm] 15.2 51.9 8.7 0.05Reactivity Yield [%] 89.3 93 92.3 — Time [min] 338 412 661 — PhysicalContained amont of — — — — properties catalyst [ppm] (Before thin-film —— — (0.07)* distillation) Existence of None None None — metallic saltaggregates Experimental example No./Reference — — — — experimentalexample No. Urethanization Time till 0.7 V [min] — — — — reaction rateTime till 1.0 V [min] — — — — Load value at 30 — — — — min [V] Loadvalue at 60 min — — — — [V] Final load value [V] — — — —

TABLE 7 Reference Reference Reference Reference example 1 example 2example 3 example 4 Experimental example No./ Experimental ReferenceReference Reference Reference experimental example experimentalexperimental experimental example No. 10-1 example 6-1 example 9-1example 10-1 Row 16 HD 50 50 50 50 materials ISB 50 50 50 50 Diol [mol%] Catalyst Type Mg(OAc)₂•4H₂O Mg(OAc)₂•4H₂O Zn(OAc)₂ Zn(OAc)₂ Usedamount 110 368 24.8 136 [ppm] Reactivity Yield [%] 95.1 95.4 90.9 88.9Time [min] 473 405 740 828 Physical Contained amont 104 350 — —properties of catalyst [ppm] (113) (315) — — (Before thin-filmdistillation) Existance of Exists Exists — — metallic salt aggregatesExperimental example Experimental Reference No./Reference experimentalexample 1 experimental example No. 0-4 example 6-4 — — Urethan- Timetill 0.7 V [min] 7 — — — ization Time till 1.0 V [min] — — — — reactionLoad value at 0.80 — — — rate 30 min [V] Load value 0.82 — — — at 60 min[V] Final load <1.0 (partial (promptly, strong — — value [V]gelatification) gelatification)

As is clear from comparison of Examples 7 to 15 with Reference examples3 and 4, relative to a case in which a compound using a metal of Group 9on the periodic table as a transesterification catalyst, when a compoundusing a metal of Group 1 or 2 on the periodic table was used, thereaction speed of the transesterification catalyst could be acceleratedto be able to obtain a polycarbonate diol product in a short time.

Furthermore, as is clear from comparison of Examples 7, 9 and 11 withReference examples 1 and 2, by using a polycarbonate diol product whichwas obtained in such a short time and contained 100 ppm or less ofcatalyst, gelation could be suppressed and a homogenerous urethane couldbe obtained, while by using a polycarbonate diol product which contained100 ppm or more catalyst for urethanization as shown in Referenceexamples 1 and 2, the urethanization reaction was further promoted thanexpected and gelation was accelerated, which did not result in ahomogeneous polyurethane. In particular, in Reference example 2, a largeamount of gel was formed right after MDI addition, and the test couldnot be continued, while in Reference example 1, it exceeded Load value0.7 V in only 10 min., the viscosity increase stopped, but gel wasformed right after MDI addition, and the urethane solution after theexperiment was an inhomogeneous solution.

On the other hand, as is clear from comparison of Example 7 with Example15, obtaining a polycarbonate diol product containing small amount ofcatalyst such as less than 0.1 ppm was difficult to obtain by atransesterification catalyst, because reactivity of diol and carbonateester were not improved enough, and little reaction progress wasrecognized. However, for example, by purifying a polycarbonate diolcontaining 0.1 ppm or more of catalyst, controlling the amount to beless than 0.1 ppm is possible. By using such a polycarbonate diol forurethanization, it is possible to suppress gelation and obtain ahomogeneous urethane.

[Consideration of Terminal A Rate (I) and Urethanization Reaction Speed]

Tables 8 shows summaries of the amount of the raw material diol whichwas used in producing the polycarbonate diol, types of catalyst, amountof catalyst, yield, the highest reaction temperature and reaction time,Terminal (A) ratio (I) in a polycarbonate diol product, and results ofurethanization reaction speed tests with a polycarbonate diol productbeing used, about the aforementioned Experimental examples 5-1, 7-1,9-1, the aforementioned Reference Experimental examples 8-1 and 10-1.

TABLE 8 Reference Reference Example 16 Example 17 example 5 example 6Experimental example No./ Experimental Experimental ExperimentalReference Reference experimental example example example experimentalexample No. 7-1 9-1 5-1 example 8-1 Row 16 HD 50 50 50 50 materials ISB50 50 50 50 Diol [mol %] Catalyst Type Mg(OAc)₂•4H₂O Mg(OAc)₂•4H₂OMg(OAc)₂•4H₂O Mg(OAc)₂•4H₂O Used amount 9.1 46 0.9 9.1 [ppm] ReactivityYield [%] 93.5 95.1 77.6 87.4 Highest 160 160 160 180 temperature [° C.]Time [min] 416 502 454 770 Physical Formula (I) 1.40 1.85 1.11 1.96properties Experimental example Experimental Experimental ExperimentalReference No./Reference experimental example example exampleexperimental example No. 7-4 9-4 5-4 example 8-4 Urethan- Time till 3310 Approx. 240 14 ization 0.7 V [min] reaction Time till 42 14 — 16 rate1.0 V [min] Load value 0.57 1.6 0.12 — at 30 min [V] Load value 1.501.80 0.21 — at 60 min [V] Final load 1.70 1.80 0.70 — value [V]

As it is clear from a comparison of Examples 16 and 17 with Referenceexample 5, when an polycarbonate diol product having Terminal (A) ratio(I) is 1.2 or more was used, it had an appropriate urethanizationreaction speed and urethanization reaction could be processed enough toobtain a polyurethane with designed physical properties. On the otherhand, it was found that when a polycarbonate diol product having 1.2 orless of Terminal (A) ratio (I) was used, urethanization reaction speedwas too slow to process urethanization reaction, and a polyurethane withdesigned physical properties such as hardness might not be obtained.Specifically, when a polycarbonate diol product having 1.2 or less ofTerminal (A) ratio (I) of Reference example 5 was used, itsurethanization reaction speed was slow and it took about 4 hours for itsload value to exceed 0.7 V, and its final load value reached only 1.0 Vor less. On the other hand, when a polycarbonate diol product having 1.2or more of Terminal (A) ratio (I) of Examples 16 and 17 was used, it hadan appropriate urethanization reaction speed, and urethanizationreaction could be processed enough, while its load value exceeds 0.7 Vwithin 60 min. and its final load value exceeded 1.0 V and then theviscosity increase stopped.

On the other hand, as is clear from a comparison of Example 16 and 17with Reference example 6, when an polycarbonate diol product havingTerminal (A) ratio (I) was 1.9 or less was used, it had an appropriateurethanization reaction speed and controlled urethanization reactioncould be processed enough to obtain a polyurethane having designedphysical properties. Also, it was found that when a polycarbonate diolproduct having more than 1.9 of Terminal (A) ratio (I) was used,urethanization reaction was processed too much due to its excessivevelocity of the reaction, and therefore a polyurethane having designedphysical properties such as hardness might not be obtained.Specifically, by comparing Example 16 with Reference example 6, even ifthey had the same amount of catalysts, but urethanization reaction speedlargely differed due to the difference of Terminal (A) ratio (I), and itis obvious that the Terminal (A) ratio (I) largely affects itsurethanization reaction speed. When a polycarbonate diol product having1.9 or more of Terminal (A) ratio (I) of Reference example 6 was used,due to its excessive velocity of the urethanization reaction itsviscosity increase did not stop after the load value reached 0.7 V in 14min. and the viscosity increased too high to measure its final loadvalue.

[Consideration of Maximum Reaction Temperature and UrethanizationReaction Speed]

Tables 9 shows summaries of the amount of the raw material diol whichwas used in producing the polycarbonate diol, and types and amount ofcatalyst, yield, the highest reaction temperature and reaction time,Terminal (A) ratio (I) of a polycarbonate diol product, and results ofurethanization reaction speed tests with a polycarbonate diol productbeing used, about the aforementioned Experimental examples 7-1 and theaforementioned Reference Experimental example 8-1.

TABLE 9 Reference Example 18 example 7 Experimental example No./Experimental Reference Reference experimental example experimentalexample No. 7-1 example 8-1 Raw materials 16 HD 50 50 Diol [mol %] ISB50 50 Catalyst Type Mg(OAc)₂•4H₂O Mg(OAc)₂•4H₂O Used amount [ppm] 9.19.4 Reactivity Yield [%] 93.5 87.4 Highest temperature [° C.] 160 180Time [min] 416 770 Physical properties Formula (I) 1.40 1.96Experimental example No./ Experimental Reference Reference experimentalexample experimental example No. 7-4 example 8-4 Urethanization Timetill 0.7 V [min] 33 14 reaction rate Time till 1.0 V [min] 42 16 Loadvalue at 30 min [V] 0.57 — Load value at 60 min [V] 1.50 — Final loadvalue [V] 1.70 —

As is clear from a comparison of Example 18 with Reference example 7,when a polycarbonate diol product, which was obtained at the highestreaction temperature was less than 180° C. during producing, anappropriate Terminal (A) ratio (I) and urethanization reaction speedwere obtained to process urethanization reaction appropriately and apolyurethane having designed physical property physical properties wasobtained. On the other hand, it was found that a polycarbonate diolproduct obtained with the highest reaction temperature of 180° C. orhigher during producing had a higher Terminal (A) ratio (I), while anurethanization reaction was conducted by using that product, itsurethanization reaction speed was too high, the urethanization reactionwas processed too much, its viscosity was increased too much to measureits load value, and a polyurethane having a designed physical propertiessuch as hardness might not be obtained.

INDUSTRIAL APPLICABILITY

A polycarbonate diol of the present invention has a rigid structure (A)in a molecular chain, therefore a polyurethane produced by using thepolycarbonate diol has high hardness, excellent abrasion resistance, andlong-term maintenance of the surface aspect, so applications to coatingagent, water-based paint, adhesive agent, synthetic leather, andartificial leather, for example is preferred. In addition, Structure (A)has a higher hydrophilic property, therefore a polyurethane produced byusing the polycarbonate diol of the present invention is industriallyquite useful because it can be appropriately used in an application inwhich an affinity to water is required, for example, an application forproducing water-based paint material with smaller environmental load.

According to the present invention, by a simple method of irradiating anactive energy ray, a cured film more excellent in mechanical strengthand contamination resistance can be easily produced, so in a field forprotecting a base material's surface by a cured film, for example, bothfurther improved productivity and higher performance of cured film canbe expected in producing the cured film by the above simple method.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

This is a continuation of International Application PCT/JP2011/059206,filed on Apr. 13, 2011, and designated the U.S., (and claims priorityfrom Japanese Patent Application No. 2010-093155, which was filed onApr. 14, 2010 and Japanese Patent Application No. 2010-191858, which wasfiled on Aug. 30, 2010) the entire contents of which are incorporatedherein by reference.

1-20. (canceled)
 21. A polycarbonate diol, obtained by reacting (i) atleast one of diols selected from isosorbide, isomannide and isoidide,(ii) a diol having 1 to 15 carbons which may contain hetero atom, and(iii) a diester carbonate, by use of a transesterification catalyst,wherein, the transesterification catalyst is either a compound using ametal of Group 1 or a compound using a metal of Group 2 on the periodictable; and the amount of the transesterification catalyst contained inthe polycarbonate diol is 100 ppm or less as the weight ratio of themetal; the polycarbonate diol has a content of a repeating unit of thefollowing formula (A) of 10 mass % or more:

the polycarbonate diol has a number average molecular weight of 500 ormore and 5,000 or less; and the average number of hydroxyl groups permolecule in the polycarbonate diol is 1.8 or more and 2.2 or less. 22.The polycarbonate diol according to claim 21, wherein the number averagemolecular weight of the polycarbonate diol is 900 or less.
 23. Thepolycarbonate diol according to claim 21, wherein the molecular weightdistribution of the polycarbonate diol is 1.5 to 2.0.
 24. Thepolycarbonate diol according to claim 21, wherein the amount of thetransesterification catalyst contained in the polycarbonate diol is 0.1ppm or more as the weight ratio of the metal.
 25. The polycarbonate diolaccording to claim 21, wherein the transesterification catalyst is acompound using a metal of Group 2 on the periodic table.
 26. Thepolycarbonate diol according to claim 21, wherein at least part of amolecular chain includes a repeating unit represented by the followingformula (A) and a repeating unit represented by the following formula(B), and the number average molecular weight is 250 or more and 900 orless, and the Terminal (A) ratio represented by the following formula(I) is 1.2 or more and 1.9 or less;

wherein X represents a divalent group having 1 to 15 carbons which maycontain hetero atom;Terminal (A) ratio (I)={(The number of structure (A) in molecular chainterminal)/(The total number of structures (A) and (B) in molecular chainterminal)}/{(The number of structure (A) in molecular chain)/(The totalnumber of structures (A) and (B) in molecular chain)}.
 27. Thepolycarbonate diol according to claim 21, wherein the diester carbonateis diphenyl carbonate.
 28. The polycarbonate diol according to claim 21,wherein the content of the diphenyl carbonate is 1 weight % or less. 29.The polycarbonate diol according to claim 21, wherein 5% or less ofmolecular chain terminals are either alkyloxy group or aryloxy groupamong all terminals of the molecular chains.
 30. The polycarbonate diolaccording to claim 21, wherein the value of Hazen color number (APHAvalue: according to JIS K0071-1) is 100 or less.
 31. The polycarbonatediol according to claim 21, wherein 95% or more of the molecular chainterminals of the polycarbonate diol are hydroxyl groups.
 32. Apolycarbonate diol, wherein at least part of a molecular chain includesa repeating unit represented by the following formula (A) and arepeating unit represented by the following formula (B), the content ofthe repeating unit of the formula (A) is 10 mass % or more, the numberaverage molecular weight is 500 or more and 5,000 or less, the averagenumber of hydroxyl groups per molecule in the polycarbonate diol is 1.8or more and 2.2 or less, and the terminal (A) ratio represented by thefollowing formula (I) is 1.2 or more and 1.9 or less;

wherein X represents a divalent group having 1 to 15 carbons which maycontain hetero atom;Terminal (A) ratio (I)={(The number of structure (A) in molecular chainterminal)/(The total number of structures (A) and (B) in molecular chainterminal)}/{(The number of structure (A) in molecular chain)/(The totalnumber of structures (A) and (B) in molecular chain)}.
 33. Thepolycarbonate diol according to claim 32, wherein the number averagemolecular weight is 500 or more and 900 or less.
 34. A polycarbonatediol producing method, comprising; reacting (i) at least one of diolsselected from isosorbide, isomannide and isoidide, (ii) a diol having 1to 15 carbons which may contain hetero atom, and (iii) a diestercarbonate, by use of a transesterification catalyst, and wherein thehighest temperature for the reaction is lower than 180° C.; and whereinthe polycarbonate diol has a content of a repeating unit of thefollowing formula (A) of 10 mass % or more:

the polycarbonate diol has a number average molecular weight of 500 ormore and 5,000 or less; and the average number of hydroxyl groups permolecule in the polycarbonate diol is 1.8 or more and 2.2 or less. 35.The polycarbonate diol obtained by the polycarbonate diol producingmethod according to claim 34.